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By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By Emil Gathmann

Through wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot. Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium, there is no commercial reason why all steel should not be thoroughly degasified. A degasified steel being provided, the method of freezing or solidifying the liquid steel into an ingot, and the subsequent working into blooms and thence into various products, is of great importance in reducing the crop or scrap portion of the steel, due to segregation and pipe. How to ac-

Jan 1, 1916

By Nelson Severinghaus

FOLLOWING the end of hostilities of World War II, a resurgence of industrial and home building has given impetus to the use of many products of the stone industry. Shortage and high prices of some building materials such as lumber have aided wider acceptance of materials such as concrete products which have been relatively plentiful and which have not risen so rapidly in price. Ingredients for many of these substituting materials come from the stone industries, often from by-products of stone operations. Most of the tonnage of the stone industry in the State of Georgia comes from granite and marble. There are extensive dimension stone operations in granite in the Elberton and in the Lithonia areas. Building and monumental marble from the Tate area has been used throughout the country. Cutting operations in both types of stone have their by-products in faulty blocks and in spalls. In the State there are three large crushed-stone plants utilizing granite, one near Camak, one near Lithonia and one at Stockbridge. All have had excess fines or screenings in the past but this excess is largely disappearing with development of new uses. At times this "waste" has amounted to as much as 20 pct of the stone quarried. Handling of this large tonnage from point of screening out to storage piles presented a costly problem and large areas were taken up by the piles. Crushed stone is generally sold with a relatively narrow margin of price over cost, so any elimination of disposal cost or increase of income by marketing of by-products is highly desirable. BY-PRODUCTS OF GRANITE DIMENSION STONE It sometimes becomes difficult to differentiate between main product and by-product. In the cutting of granite dimension stone in the Lithonia district of Georgia, a considerable quantity of remnants of uneven shape and size is produced. The larger of these pieces have long found use as building rubble, particularly for retaining walls and building foundations (Fig I). They are broken down to one man size by plug drilling and wedging and by hammer. In recent times, demand for this former by-product has grown so that quarries have been opened for the production of rubble as a main product. Local masons have attained skill in using these irregular shapes to form economical and attractive walls. Areas such as Elberton, Georgia, which do not have a large building market nearby, tend to accumulate piles of large pieces of reject stone. When a road job or other local construction offers a quantity market for crushed stone, a portable crusher works this material down to crushed aggregate. Spalls and finer chips from granite stone-cutting operations have generally found their way into crushers and thence to the many uses for crushed aggregate. One company near Lithonia started marketing the smaller by-product crushed sizes for chicken grit about ten years ago. This use has grown to nation-wide distribution and the tonnage is now so great that they have opened a large quarry with

Jan 1, 1947

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By William A. West

One manifestation of anelastic properties in solids is the mechanical elastic aftereffect, which may be described briefly as follows: If a stress is applied to a solid body, a deformation or strain is produced. On removal of the stress, this deformation disappears, at least in part. As a first approximation, this appearance or disappearance of deformation usually has been considered instantaneous. Actually, however, for a very wide variety of substances, on application of stress the instantaneous deformation is followed by a further slow yielding, which continues, although at a rapidly diminishing rate, for as long as the stress is applied. Similarly, on removal of the stress, the instantaneous recovery from deformation is followed by a further slow recovery, which continues, although at a rapidly diminishing rate, often for a long time. This latter phenomenon has been called the "elastic after-effect." Experiments upon the elastic after-effect in metals, when properly designed and when properly interpreted, are capable of giving quite precise information regarding the relation between stress and strain in the various constituent parts of the metal. For example, if certain parts of the metal, such as grain boundaries or slip bands, behave in a viscous manner—that is, if therein—the relaxation spectrum will contain lines or bands associated with the relaxation of shear stress within these parts. No attempts have heretofore been made to utilize elastic after-effects for obtaining such detailed information. The purpose of the present paper is to explore the possibilities of properly designed and interpreted experiments on the elastic aftereffect in metals. Since new procedures and principles are employed in this study, an attempt has been made to record each step taken. Elastic after-effect observations are susceptible of simple interpretation only when the stress level employed is so low that all effects are linear with the stress. Just how low the stress level must be can he determined only by experiment. An advnntage, other than simple interpretation, is associated with low stress levels. When all effects are linear, derived quantities, such as the relaxation spectrum, are independent of the stress distribution. It is, furthermore, possible to employ the type of deformation that is most convenient from the experimental standpoint; for example torsion. It appears that in experiments involving both loading and unloading the following would be observed: I. Instantaneous deformation, recoverable instantaneously in whole, or in part. 2. Delayed deformation, recoverable slowly in whole, in part, or not at all. 3. Permanent deformation, the difference between total deformation and total recovery. In the work here described, unloading experiments only were made. Wires were

Jan 1, 1947

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By John G. Hall

The pumping operations at the Chief mine have been unique in the respect that for many years the entire flow of water into the mine has been disposed of by pumping into natural underground "caverns" or "sinks." Volumes up to 4000 gpm have been pumped into these caverns with no apparent tendency for the caverns to fill with water, and it has never been proven that any of the water returns to the mine workings. Major pumping operations have been carried on during two periods, the first from 1918 to 1927, and the second from 1942 to the present time. Early Pumping Operations CHIEF MINE The Chief Consolidated Mining Co. was organized in 1909, and for the following nine years ore was developed and mined from the 600 level down to the 1800 level, all above the permanent water table, the 1820 level. The ore occurs as extremely-irregular pipes of replacement ore in limestone, and to date a total of approximately 2 1/2 million tons of ore has been produced. The ore was highly oxidized down to the permanent water level, and some highly-oxidized ore runs occur beneath the permanent water table. In 1916, with extensive mining being done on the 1800 level, 20 ft above the water table, there were indications that a zone of secondary enrichment might exist below the water, and in order to follow the ore runs to greater depth, it was realized that arrangements would have to be Made to pump water to the surface. The original pumping installation was designed to pump 350 gpm in five stages against a 1900-ft head to the surface. By January 1919, the water had been lowered to the 1900 level and an excellent grade of silver-lead ore was being produced from the zone of secondary enrichment. At this point. the flow of water equalled the capacity of the pumps, and pumps of an additional 1000 gpln were installed to supplement the original system. By January 1920, the water had been lowered approximately 100 ft, and the total flow of water was 1000 gpm. The water was being pumped from many different places in the mine where ore was being followed downward, with 27 different pumps operating below the 1800 level, mainly Cameron air-driven sinker pumps. These first sinking pumps were cumbersome and inefficient, and each of the larger pumps weighed approximately three tons and required tremeridous volumes of compressed air. During this period, an exploration drift being extended north and west from the Chief shaft on the 1600 level encountered a large natural cavern some 2000 ft from the shaft. This cavern in places measured 60 ft in diameter. Sometime later the disposing of water into this cavern was suggested, and as an experiment to determine the results of such an operation, an attempt was Made to fill the cavern by pumping in a small volume of water, but the water disappeared as fast as it was discharged into the cavern. It was decided then to try the cavern as a drainage outlet for the entire volume of water being pumped to the surface, and the water apparently did not return to the mine workings. Subsequently water up to 3000 gpm was pumped into this cavern. An attempt was made to determine whether any water was being returned from the cavern to the lower workings, and 100 lb of sodium fluorescein salt was added to the water discharged into the cavern, but no trace of it was found in the drainage water in the mine. Results of another such test will be described later.

Jan 1, 1950

By J. E. Drury, W. M. Byers, E. J. Lynch

Measurements made with starch ~~~~s indicate that the Presence of starch serves to depress the streaming potential of a clay mud system. Measurements with pure starch slurries show that the addition of NaCl or CaO reduces the streaming potential significantly. The addition of NaOH, however, causes only a minor reduction in potential even when there are large changes in mud resistivity. INTRODUCTION In their excellent study of the streaming potential, Hill and Anderson' proposed that the presence of conductive solids within the filter medium will reduce the generated potential. This theory was demonstrated with measurements on shaly sandstone cores having various "b" factors; the cores with the higher negative b factors showed markedly lower potentials. (The factor b was originally defined by Hill and Milburn2 in an expression relating the resistivity of a shaly sandstone to the resistivity of the interstitial water: log F, = log F,, + b (log 100R,)'. 'he factor b, therefore, is a measure of the contribution of the conductive solids to the total conductivity of the sample. It has been found experimentally to be directly related to the amount of chemically exchangeable ion per unit pore volume.) In the logical extension of this hypothesis to the streaming potential created by filtration through mud cakes, they suggested that the presence of nonconductive starch in a drilling mud would have the opposite effect; i.e., it would cause the streaming POtential to be increased. The high streaming potentials that they observed with lime muds were attributed to this cause. A cross-plot of some of their results which are relevant to this discussion is given in Fig. 1. The lime-mud curves and untreated-mud curve are taken from curves given in their paper. The gyp-mud line was estimated from their statement that the measured streaming potential for gyp muds in the range of 1.5 to 2.0 ohm-m was approximately 18 mv/1,000 psi. These gyp-mud potentials were the lowest that they reported for any of the bentonitic-clay muds, and were the only ones which were less than the untreated-mud potentials. This very low streaming potential of gyp muds has also been observed in field studies.' By way of comparison, a U. of Texas publication4 gives the approxi-ate compositions for lime and gyp muds shown in Table 1. These materials are added to a bentonitic-clay mud base. It can be seen that both of these muds contain significant amounts of calcium salts and that the gyp mud has the higher concentration of starch. It would appear from this and from the data shown in Fig. 1 that starch may well be the cause of a streaming-potential reduction, rather than a potential increase. EXPERIMENTAL A series of streaming-potential experiments has been performed using a cell of a design similar to that reported by Wyllie.5 Calomel electrodes were used in both the mud slurry and the filtrate. Pressure in the cell was generated with high-pressure nitrogen. The primary objective of the investigation was to determine the effect of starch on the potential. Five different slurries were made which ranged in composition from untreated ben-tonitic mud (Baroid Aquagel) to a pure starch suspension (Baroid Im-permex). The intermediate slurries were prepared by mixing together a 9-lb/bbl clay mud with a 12-lb/bbl starch suspension in the ratios 1:3, 1:1 and 3:1. When starch was used alone, it was necessary to use an 18-Ib/bbl mixture, since leaner mixtures would not form a suitable filter cake. The clay mud used in the experiments was aged for three months before use. In addition to this series of measurements on the starch-clay mud mixtures, other experiments were performed to determine the effect on the potential of the absolute starch and Aquagel concentration, and the effect of adding various chemicals. RESULTS The effect of starch on the streaming potential is shown clcarly in Fig 2. Increasing percentages of starch resulted in n continually decreasing

By B. Chalmers, Stefan Wojciechowski

Rotary oscillation of the mold has been used to produce mechanical stirring of the melt during unidirectional solidification. Al-Cu alloys (1 to 4 wt pct Cu) were solidified to study the influence of alloy composition, temperature at which intensive cooling was initiated, and intensity of stirring on the temperature distribution in the sample, the resulting structure, and the copper microsegregation at the columnar to equiaxed transition. The Proposed explanation for the equiaxed solidification in stirred castings consists of the melting off of dendrite fragments, their partial remelting in hotter liquid, and the subsequent growth of the surviving part when the temperature of the melt is lowered. This may result in the formation of a crystal network, which can stop the growth of the columnar crystals and produce the equiaxed zone. It has long been known and many times affirmed that ultrasonic vibrations or relative motion of liquid and solid can significantly reduce the length of the columnar zone and refine the grains in the equiaxed zone in ingots and castings. Because of the technological importance of these phenomena many investigations have been conducted in which ultrasonic energy or mechanical vibration,1-6 electromagnetic stirring,7"10'17 magnetic stirring,"'12 or mechanical stirring13'14 were used to produce the relative liquid-solid motion. More recently, the question of the importance of natural (or thermal) convection has been raised.15-l7 Several possible mechanisms have been suggested.l,8,18-20 They can be divided into two main groups. The first group includes such nucleation hypotheses as nucleation frequency enhancement due to cavitation at the mold wall or other surfaces; cavita-tion in the body of the liquid resulting from the pressure wave, or an agglomeration mechanism, which involves the formation of nuclei by the accretion of subcritical nuclei. The second group considers the grain-refining action to be due to crystal multiplication phenomena such as the removal of the dendrite fragments by viscous forces or by a high-pressure cycle following cavitation or by a melting-off process. Sbme recent investigations give good experimental support to the melting-off proposa1.21-23 The purpose of the present study was to examine the effect of mechanical stirring during the unidirectional solidification on the structure of alloy samples and on the solidification variables. The motion of the liquid was produced by rotary oscillation of the mold around its vertical axis.

Jan 1, 1969

By A. B. Cummins

THE past year has been of unusual interest for industrial minerals. It is increasingly evident that requirements for these raw materials move with general economic trends. Thus, with a peak year in the construction, chemical and petroleum industries, the nonmetallic mineral industries have been brought into the complex maze of an economy in which military spending is in the billions and in which the national income and wholesale commodity prices reached new levels. Many industrial minerals are of first rank essentiality in the defense effort and its supporting industries, and since some of these are of limited supply and others dependent on imports, the problems of procurement, distribution and conservation of available supplies make a complicated pattern. Despite some drawbacks and weak spots, the industrial mineral industries have, in general, met the national situation with great credit and many new production records have been set. The general accomplishment in 1951 should be one of satisfaction with confidence for the future. Difficulties, unsolved problems and uncertainties should not obscure the general trend which many consider optimistic. Prices in the main have been upward, in line with the inflation spiral, but nonmetallics appear with some exceptions to be behind the general increases. Labor difficulties have not been serious throughout the year. Retarding influences in expansions and planning have been the uncertainty of the Korean and international situations and a lack of confidence by many in the government economic program and its ultimate impact on the economic structure. It must also be kept in mind that stockpiling, unless all-out war develops, reaches a level and then ceases to be a major sustaining factor in the mineral markets. In accordance with the Defense Production Act of 1950 various control agencies have been set up to establish the desired rate of stockpile acquisitions. The objectives are subject to change depending on availabilities and needs-military, industrial, and civilian. In some minerals there has been disagreement on actual stockpile requirements, and there is some feeling that the needs of defense might be better met if more funds went into the development of new sources of supply of scarce raw materials and more materials were released to industry at this time. Nonmetallic minerals on the strategic and critical list of the Munitions Board as of July 1951 were: Group I; asbestos, some types; bauxite, refractory grade; beryl; celestite; chromite, chemical and refractory grades; columbite; corundum; diamonds, industrial; fluorspar, acid grade; graphite, some types; kyanite; manganese ore, battery and chemical grades; mica, some types; quartz crystals; rare earths; sapphire and ruby; talc, steatite, block; and Group II; bauxite, abrasive; cryolite, natural; diamond dies; graphite, crystalline fines; iodine; mica, muscovite block, stained and lower; rutile; selenium; talc, steatite, ground; zirconium ore, zircon. Details on the current status of stockpiling inventories are not available. The Defense Minerals Exploration Administration has, since April, executed 39 contracts for the exploration of nonmetallic minerals, including twenty for mica, seven for beryl-mica, six for asbestos, three for sulphur and one each for monazite, steatite talc and fluorspar. Total value of these contracts came to $892,059, of which the Government's participation amounts to $689,247. There were on hand at year's end another 97 applications for exploration aid on nonmetallic minerals in twenty different

Jan 1, 1952

By Gordon I. Gould

The treatment of quicksilver ores to extract the metal, for centuries one of the fundamentally simpler metallurgical operations, has undergone few if any material changes during the past iew decades other than improvement and change of type of equipment used. Of almost universal application and as the seldom deviated from process, the roasting method is still considered superior to chemical metallurgy. Likewise, roasting of the crude ore without previous beneficiation continues to be standard practice, although some successful operations have employed concentration prior to roasting. The roasting process has been carried out in a variety of equipment, devised for different tonnage capacities, to treat "special" ores, and to satisfy an inventive notion of the particular builder, but during the past 25 years there has been one outstanding change in roasting equipment. This change, though neither originating in nor confined to the United States, has probably been developed and applied to a far greater extent in this country than in any other mercury-producing country of the world. The change from manually or gravity operated furnaces, mostly huge brickwork affairs justified largely by simplicity, lack of power and mechanical requirements, and occasionally by excellent metallurgical results, to mechanical furnaces, began actively during World War I under the stress of requirements for in- creased production, a shortage of labor, 2nd other factors to be brought out later. During the twenties the change to mechanical furnaces became nearly complete at American mines with the development of several types, the rotary furnace predominating. During the thirties, and the period of low prices in the early part of this period, few changes were made other than mechanical improvements and an almost complete acceptance of two types: the rotary furnace and the hearth or Wedge furnace. These two types have been developed to a high degree of metallurgical efficiency, have proved to be mechanically simple and have far greater flexibility and lower operating costs than pre-World War I furnaces. Of the two types the rotary is the more popular, about 30 rotaries having been in operation in the United States in 1943 as compared with about six hearth-type furnaces. The units of smaller capacity for roasting mercury ores have almost without exception been indirectly fired, such distinction being commonly accepted as the difference between retorts and furnaces, which are fired directly. The difference between indirect and direct firing obviously permits of quite different conditions surrounding the ore being roasted in relation to the chemical reaction to take place. In the indirect-fired unit the ore is contained within the body of the retort in a stagnant if not completely oxygen-impoverished atmosphere. In the direct-fired furnace the ore is in contact with the gases of combustion, which may easily (if not too easily) be supplied with an excess of

Jan 1, 1944

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By Michael Perch, Charles C. Russell

The fact that coal is a complex organic material and heterogeneous in composition has made its study extremely difficult, particularly in regard to obtaining a fundamental concept of the processes involved in the formation of coke. It has been stated1 recently that coals are natural polymers and that in a complex reaction such as occurs during carbonization the differences between coals are quantitative and not qualitative. Such being the case, it would be expected, therefore, that a series of coals subjected to exactly the same conditions of coking would produce results that should be related quantitatively to the chemical analyses of the individual coals. In the past, however, this fact was not generally recognized and consequently many empirical test methods were devised for testing coals. The interpretation of the results obtained depended upon comparing a set of data with other data on coals of known characteristics. The testing procedure had to be conducted in precisely the same manner each time and not the least requirement in making the interpretation was experience. The test methods varied from those utilizing a gram of coal to the plant-scale tests in which one or more ovens were charged with the test coal. The aim had been principally to find some simple, inexpensive means by which the coke-making and other properties of coal could be predicted. It is not necessary to emphasize the importance of these endeavors, for anyone acquainted with the problems involved in the selection of coals for making coke is well aware of the time and expense involved in making a series of definitive tests. Several attempts have been made to derive formulas for such predictions. The relations of both ultimate and proximate analyses to coke physical properties and byproduct yields have been studied. Lowry and co-workers1 correlated statistically the U. S. Bureau of Mines-American Gas Association assay test results with coal analyses, using 90 coals and coal blends. Parry,² Spooner,3 and Gabinskii and Krym4 made similar correlations. Lowry concluded that there were definite relationships between the proximate analyses of the coals and the yields and properties of the products. Although this statistical study was made on test results from carbonizing coal in a cylindrical steel retort, the conclusions are important and provided one of the first steps in the simplification of this complex subject. Studies should be made of other references on this subject just cited. Studies of the coking process reported in the literature frequently were confined to a small number of coals, and very few have included coals from various ranks. It would seem logical, however, that a program for studying factors involved in the formation of coke should be based on a number of coals selected from each of the various classes or types of coking coal. The possible use of the scheme of classifi-

Jan 1, 1950

By Edward B. Walker, Michel Grosmangin

The geological and economic conditions peculiar to the Greater Oficina area are presented to demonstrate the necessity of a low-cost, well-site method of distinguishing gas-bearing formations. The method of gas detection with the neutron log is briefly discussed and its limitations are explained. A new method is described which consists in running a second neutron log with a larger source-to-detector spacing. Field data indicate that under favorable conditions the larger spacing response is proportionately more influenced by the virgin gas zone than is the shorter spacing response. One important condition is that the gas sands be invaded, with a diameter of invasion equal to about two to three times the hole diameter. The calibration of the longer spacing log is made so that the two logs read the same deflection in shale and in a known water or oil sand. Under such conditions, gas is indicated by a positive separation, i.e., the curve for the longer device is displaced to the right of the curve for the shorter device. Because of the non-linearity of the long spacing response, low porosity formations also show positive separations. In sands with large porosity variations, the gas sands can no longer he located visually. They can be detected on a plot of shorter spacing vs longer spac-ing deflections. INTRODUCTION In the Greater Oficina area of Eastern Venezuela, the rapid and accurate detection of gas from well logs is of primary importance because of a combination of economic, geologic, and operational conditions. Briefly, these conditions are: economic—there is no market for gas at the present time; geologic—a single well may contain as many as 30 or more oil or gas sands for which intervals -to be tested must be selected; opera-tional—first, once opened to the casing through perforations, gas sands are extremely difficult and expensive to squeeze off, and second, gas detection must be rapid because the geologist must decide immediately, at the well, which sand to perforate. During the early period of exploitation in Greater Ofi-cina, when clay base muds were used, sidewall samples, together with electric logs, gave fairly good distinction between oil and gas sands. When exploitation became concentrated on deep fields of poorer sidewall sample recovery, and after the advent of oil emulsion muds, now the standard drilling fluid in Greater Oficina, the regular neutron log became the most reliable indicator of gas. In 1953, R. Norelius devised the dual-spacing neutron technique for gas detection. The dual-spacing neutron log has proved to be highly successful in detecting gas and has been adopted as a regular survey by all of the oil companies of the area. Several hundred dual-spacing neutron logs have been run in Eastern Venezuela and several tests per well are available for positive evaluation of the logs. The findings outlined below are based upon this extensive field experience. GEOLOGICAL CONDITIONS OF THE GREATER OFICINA AREA The Greater Oficina area lies on the south flank of the Eastern Venezuela Basin (Fig. 1). Nearly all accumulations of oil and gas in the area are trapped, in whole or in part, against normal faults. All known oil and gas reservoirs in Greater Oficina occur in the Ofi-cina formation (Miocene-Oligocene) or in the "U" sands. The U sands are the lithologic equivalent of the Merecure group (Otigocene-Eocene), which contains oil in many fields north of Greater Oficina. Most of the petroleum produced in Eastern Venezuela is from the Oficina formation.

Jan 1, 1958

By E. E. Wahlstrom

The Harold D. Roberts tunnel, in Summit and Park Counties, Colorado, is a concrete-lined pressure tunnel finished to a circular cross section of 10.25 ft diam. The tunnel is 23.3 miles long and is designed to transport water for domestic use by the City and County of Denver from reservoir storage at Dillon to a tributary of the South Platte River at Grant. The tunnel passes beneath the Continental Divide at the crest of the Front Range and intersects rocks of diverse types and origins and geologic structures of extreme complexity. Geologic investigations preceded and were continued during construction and contributed materially to the safe and economical advance of the tunnel headings. Geological data obtained and evaluated during construction include plans and sections on a scale of 1 in. to 50 ft, rock temperatures at 2000-ft intervals, records of progress related to geology, records of ground-water conditions, summaries of the use of steel and timber supports, and summaries of grouting operations. Adverse conditions required use of steel and timber supports for 71.74% of the total length of the tunnel. Most supported sections reached a condition of equilibrium within a few hours to a few months after being excavated, and the concrete lining serves chiefly to provide an additional safety factor and to provide necessary hydraulic characteristics to the tunnel. Efforts to attain a maximum rate of advance of the tunnel headings necessitated use of more steel and timber supports than would have been required in a less accelerated tunneling operation. This report summarizes geologic investigations prior to and during construction of the Harold D. Roberts tunnel in Summit and Park Counties, Colorado (Fig. 1) and analyzes the tunneling operation as it is related to the various kinds of geologic conditions encountered in the tunnel. The tunnel is concrete lined to a circular cross section of 10.25 ft and is designed to transport 788 sec ft from reservoir storage at Dillon 23.3 miles along a dog-leg course passing under the Continental Divide to outlet and control works at Grant, Colo. The primary purpose of the tunnel is to augment the domestic water supply of the City and County of Denver, but plans include provisions for power generation at the outlet portal at a future date. Location of the tunnel was made after extensive preliminary geologic and engineering investigations by the Board of Water Commissioners of the City and County of Denver, and the U.S. Bureau of Reclamation. In 1946 the Board of Water Commissioners started tunnel driving on a limited scale from the east (outlet) portal and by 1955 had completed 9986 ft of tunnel. An urgent need for additional sources of water supply required acceleration of the tunneling operation, and, in 1955, Tipton and Kalmbach Inc. of Denver were assigned the responsibility of reviewing the project and preparing plans and specifications for the tunnel and appurtenant features. Additional geologic studies were made, and the geology of several possible alternate tunnel lines were compared before determining that the tunnel should be driven along the course previously adopted by the Board of Water Commissioners. On July 12, 1956, a contract for construction was awarded to Blue River Constructors Inc., a combine

Jan 1, 1962

By J. R. Kyte, C. C. Mattax

Previous workers have developed differential equations to describe oil displacement by water imbibition, but have not explicitly defined the relationship between recovery behavior for a single reservoir matrix block and its size. In the present work, imbibition theory is extended to show that the time required to recover a given fraction of the oil from a matrix block is proportional to the square of the distance between fractures. Using this relationship, recovery behavior for a large reservoir matrix block is predicted from an imbibition test on a small reservoir core sample. The prediction is then extended to analyze recovery behavior for fractured- matrix, water- drive reservoirs in which imbibition is the dominant oil-producing mechanism. Experimental data are presented to support the basic imbibition theory relating matrix block size, fluid viscosity level and permeability to recovery behavior. INTRODUCTION Imbibition has long been recognized as an important factor in recovering oil from water-wet, fractured-matrix reservoirs subjected to water flood or water drive. l-3 Recently, two approaches have been published which might be used to predict imbibition oil-recovery behavior for reservoir-sized matrix blocks. Graham and Richardson4 used a synthetic model to scale a single element of a fractured-matrix reservoir. lair,' on the other hand, used numerical techniques to solve the differential equations describing imbibition in linear and radial systems. This latter method requires auxiliary experimental data in the form of capillary pressure and relative permeability functions. These two approaches, i.e., synthetic models and numerical techniques, have been used to study a variety of reservoir fluid-flow problems. One pur- pose of this work is to present, with experimental verification, a third method for predicting imbibition oil recovery for large reservoir matrix blocks. This method uses scaled imbibition tests on small reservoir core samples to predict field performance. The imbibition tests are easier to perform than the capillary pressure and relative permeability tests required to apply the numerical method. Furthermore, when suitably preserved reservoir-rock samples are used, the properties of the laboratory system are the same as those of the field. This offers an important advantage over the use of synthetic models because there is usually some question as to how accurately reservoir-rock properties can be duplicated in such models. Based on the recovery behavior for a unit matrix block, an analysis is presented to predict oil recovery for a fractured, water-drive reservoir made up of many such unit blocks. In the analysis, it is assumed that the flow resistance and the volume of the reservoir fracture system are negligible compared with that of the porous matrix. These assumptions are generally consistent with observed characteristics of many fractured-matrix reservoirs, and have been employed in previous studies.2,3,6-8 further assumed that the effect of gravity on flow in the matrix blocks is negligible. On first thought, the latter assumption might appear to seriously limit application of the method. However, in a fractured reservoir, the effect of gravity on flow in a matrix block will be restricted by the height of the block. Furthermore, matrix permeabilities are often very low (10 md or less) in such reservoirs. This means that capillary or imbibition forces will be large, thus tending to minimize the relative importance of gravity. For these reasons, imbibition should be the dominant oil-recovery mechanism in many fractured-matrix, water-drive reservoirs. The predictive method presented in this report is applicable to such reservoirs. SCALING IMBIBITION THEORY The "scaling laws" applicable to the operation.

By Edwards Wichers

The purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcorning paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature. Treatment of Platinum Ore As is well known, the principal source of the platinum metals is a mixture of several native alloys of the metals, found chiefly in naturally concentrated deposits in stream beds or alluvial material. Without attempting to enumerate all of the minerals present, it may be said that the concentrated ore from such sources contains all of the six platinum

Jan 1, 1928

By V. W. Aubel

Among the iron-bearing ores of the world, the titaniferous iron sands of New Zealand are probably the least known to American engineers. This is not surprising in view of the fact that American ironmasters look with disfavor on any, even domestic, ores containing over 1 per cent. titanium. The possibilities of smelting titanium-bearing ores in the blast furnace are still undetermined, but the problem of their efficient reduction is becoming more important each year. There seems to be little inclination on the part of American furnace operators to tackle this problem, and they will no doubt continue to utilize the non-titanium ores at their command, leaving research and experiment to those countries not so fortunately endowed. New Zealand has, however, been intensely interested in her deposits of titanium-bearing iron sand, and during the last 50 years considerable English and New Zealand capital has been expended on this problem. The extent of the New Zealand iron-sand deposits is almost beyond measure. From Patea north to Manuka Heads, along almost the entire west coast of the North Island, these deposits exist. Wherever there is beach sand along this 300 mi. of coast line, the sand is iron bearing. It varies considerably in grade; but wherever the contour of the coast affords small bays and inlets, large dunes are found that are remarkably uniform in quality. Several of these large deposits, especially those at New Plymouth and Patea, are noted for their high iron content. The dune at New Plymouth runs between 55 and 60 per cent. of metallic iron; the panning action of the prevailing westerly winds and northwesterly currents has no doubt resulted in this concentration. Whatever the origin of this material may be, there is no doubt that deposition is going on continuously. At New Plymouth, a small artificial harbor, protected from the drifting sand by a large breakwall, has been dredged. Here sailing vessels have for years been loaded with iron sand for ballast by means of a crane and grab bucket operated from the wall of the breakwater. Thousands of tons of sand have been removed from this spot yet each succeeding storm renews the supply. The sand dune shown in Fig. 1 has been tested to a depth of 50 ft. (15 m.) without losing its

Jan 1, 1920