Search Documents

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By Max C. Eastman, V. H. Wilhelm

California had a record year in production and drilling activity, but the results have not been sufficient to keep up with the enormous increase in demand due to war activity. During the year, 164 dry wildcats were drilled, 80 dry wells in proved areas, 31 gas wells, and 1158 successful oil-well completions for a total of 1433 wells, compared with a total of 765 in 1942. With new discoveries of only 20,000,000 and production of 283,000,000 bbl. for the year, total reserves of California oil have decreased more than 250,000,000 bbl. However, revised estimates of the reserves of old fields indicate an increase in the state's reserves of I00,000,000 barrels. The completion of 1158 wells has served only to maintain the maximum efficient daily rate of production at 800,000 barrels. There is evidence in many fields that oil is being withdrawn too rapidly to obtain the maximum recovery, and more rapidly than is conducive to good production practice. Statistics for 1943 as compared with I942 are shown in the table in the next column, Supply and Demand Steadily mounting needs of the military forces and increased industrial consumption raised total demand for all petroleum products on the Pacific Coast to 914,000 bbl. daily in 1943. That all-time record demand was 149,ooo bbl. daily higher than in 1942 and 214,000 bbl. daily above 1941 demand. Despite restrictions due to shortages of critical material, crude-oil production was boosted from 680,000 bbl. daily in 1942 to 779,000 bbl. daily in 1943, the highest level in 15 years. However, the new crude supply plus natural gasoline production and imports from other states totaled only 840,000 bbl. daily, leaving a deficiency between supply and demand of 74,000 bbl. daily. That shortage had to be made up by withdrawals from inventories, which had been steadily depleted during the previous four years. Aboveground reserves, which totaled 159,574,000 bbl. on Jan. I, 1939, were down to ~8.000,000, bbl. at the end of 1943. Significantly enough, the greater part of that decrease occurred during the last six months of I9437 when more than 23,000,000 bbl. was taken from inventories of both crude and products. Although the size of total inventories on Dec. 31, 1943 might appear substantial, about 65 per

Jan 1, 1944

By Max C. Eastman, V. H. Wilhelm

California had a record year in production and drilling activity, but the results have not been sufficient to keep up with the enormous increase in demand due to war activity. During the year, 164 dry wildcats were drilled, 80 dry wells in proved areas, 31 gas wells, and 1158 successful oil-well completions for a total of 1433 wells, compared with a total of 765 in 1942. With new discoveries of only 20,000,000 and production of 283,000,000 bbl. for the year, total reserves of California oil have decreased more than 250,000,000 bbl. However, revised estimates of the reserves of old fields indicate an increase in the state's reserves of I00,000,000 barrels. The completion of 1158 wells has served only to maintain the maximum efficient daily rate of production at 800,000 barrels. There is evidence in many fields that oil is being withdrawn too rapidly to obtain the maximum recovery, and more rapidly than is conducive to good production practice. Statistics for 1943 as compared with I942 are shown in the table in the next column, Supply and Demand Steadily mounting needs of the military forces and increased industrial consumption raised total demand for all petroleum products on the Pacific Coast to 914,000 bbl. daily in 1943. That all-time record demand was 149,ooo bbl. daily higher than in 1942 and 214,000 bbl. daily above 1941 demand. Despite restrictions due to shortages of critical material, crude-oil production was boosted from 680,000 bbl. daily in 1942 to 779,000 bbl. daily in 1943, the highest level in 15 years. However, the new crude supply plus natural gasoline production and imports from other states totaled only 840,000 bbl. daily, leaving a deficiency between supply and demand of 74,000 bbl. daily. That shortage had to be made up by withdrawals from inventories, which had been steadily depleted during the previous four years. Aboveground reserves, which totaled 159,574,000 bbl. on Jan. I, 1939, were down to ~8.000,000, bbl. at the end of 1943. Significantly enough, the greater part of that decrease occurred during the last six months of I9437 when more than 23,000,000 bbl. was taken from inventories of both crude and products. Although the size of total inventories on Dec. 31, 1943 might appear substantial, about 65 per

Jan 1, 1944

By R. W. Fountain, W. D. Forgeng

A new constitutional diagram is presented for the cobalt-rich end of the cobalt-titaniurn system. The modifications result from the presence of a new, intermediate, fcc phase, ?, the existence and homogeneity limits of which were established by metallo-graphic and X-ray studies of alloys containing from about 3 to 30 pct Ti. The precipitation of the ? phase from supersaturated solid solution was studied by hardness and electrical resistivity measzsrements, and two distinct stages in the process were observed. COBALT forms the base for a number of precipitation -hardenable alloy systems which may be divided into two distinct categories of practical interest, a) those hardened by intermetallic compounds and b) those hardened by carbide formation. The precipitation of intermetallic compounds from solid solution in cobalt-rich alloys has, however, received very little attention. Although the phase diagrams for some binary systems capable of precipitation have been determined,' there is an almost complete lack of data on the property changes associated with the precipitation, and even less information on the kinetics of the reactions or morphology of the products. More information is available on the precipitation of carbides because of the practical significance in superalloys. A survey of cobalt binary phase diagrams suggested that the cobalt-titanium alloys might provide interesting and useful precipitation-hardenable alloys. The equilibrium diagram as proposed by Wallbaum2 is shown in Fig. 1. Köster and wagner3 have indicated that the maximum solubility of titanium in cobalt is about 10 pct at the eutectic temperature (1135oC), and this decreases to about 7.2 pct at room temperature. The temperature of the allotropic transformation in cobalt is lowered by the addition of titanium, about 5 pct being sufficient to retain the high-temperature fcc modification to room temperature. Wallbaum and Witte 4,5 have indicated that the precipitating phase in alloys containing up to about 29 pct Ti is Co2Ti, a hexagonal Laves phase of the MgNi, type. With slightly higher titanium contents, they also report a cubic modification of Co2Ti of the MgCu2-type Laves phase. Duwez and Taylor6 confirmed the existence of the hexagonal (MgNi2) modification but not the cubic (MgCuz) modification of Co2Ti and suggested that existence of the cubic form may have resulted from impurities in Wallbaum's alloys. In their work on Laves-type phases, Elliott and Rostoker 7 reported the cubic modification of Co,Ti, but did not confirm the existence of the hexagonal modification. However, Dwight8 in a discussion of the work of Eliott and Rostoker again showed the existence of both modifications of Co2Ti, a result which was confirmed at that time by Elliott and Rostoker. As a result of a study on the iron-cobalt-titanium system, Köster and Gellers suggested the existence of a Co3Ti phase isomorphous with Fe3Ti. Witte and Wallbaum,' however, established the fact that no compound, Fe3Ti, exists in the iron-titanium system, and in a later publication, wallbaum2 stated that Kitster and Geller's reasoning was not valid, and no compound, Co3Ti, exists. This conclusion was later acknowledged by Köster.10 Preliminary experiments by the present authors to determine the precipitation-hardening characteristics of the cobalt-rich, cobalt-titanium alloys re-

Jan 1, 1960

By V. M. Karve, K. K. Majundar, K. V. Viswanathan, J. Y. Somnay

The effect of calcium, magnesium, iron (both ferrous and ferric) and aluminum ions, which are commonly encountered in a typical beryl ore, was studied in the flotation of pure beryl, soda-feldspar and quartz. The vacuumatic flotation technique was employed. With sodium oleate as collector and in the absence of any activator, beryl floated in a pH range of 3 to 7.5, whereas feldspar and quartz did not float at any pH up to 11.5. The pH range of flotation increased in the presence of the ions studied. With calcium and magnesium ions beryl floated from 3 to 11.5 pH and beyond, soda-feldspar floated beyond pH 6 and quartz floated beyond pH 8. Ferrous ion activation was found to be similar to that of calcium and magnesium. Activation by ferric and aluminium ions was found to be complex and the lower and upper critical pH for all the three minerals was around 2 and 10 respectively. These studies indicated the possibility of separation of beryl from feldspar and quartz even in the presence of calcium, magnesium and ferrous ions between pH 4 and 6. Flotation tests on a mixed feed of pure minerals in a 10 g cell revealed that beryl can be selectively floated from feldspar and quartz if ferric ion is reduced to ferrous state or if it is complexed. Beryl occurs mostly in pegmatites, and hence is associated with feldspar, quartz and micas and small amounts of other minerals such as apatite and tourmaline. The separation of beryl from these minerals is difficult because all the silicates accompanying beryl have more or less the same physical properties. Specific gravities of beryl, feldspar and quartz are 2.70, 2.56 and 2.66 respectively. Electrostatic separation has been suggested but no work has been reported. ' The adsorption of sodium tri-decylate tagged with Cl4 on beryl, feldspar and quartz reveal similarity in surface properties. Much work has been reported on the flotation of beryl from ores, either directly or indirectly as a by-product, but little is known about the fundamental aspects of beryl flotation. Kennedy and O'Meara3 laid emphasis on prior cleaning of the mineral surfaces with HF. Mica is removed first by flotation of beryl with oleic acid, around neutral pH. Runke4 introduced calcium hypochlorite conditioning in a final separation stage for activating beryl in a mixed beryl-feldspar concentrate, and after washing to remove the hypochlorite, floated beryl with petroleum sulphonate. The Snedden and Gibbs5 procedure is somewhat similar to that of Kennedy and O'Meara. Emulsified oleic acid is used as collector. Recently Fuerstenau and Bhappu6 studied the flotation of beryl, feldspar and quartz with petroleum sulfonate in the presence of activators and stressed the importance of iron in the flotation of beryl. From the studies conducted in this laboratory, it was found that feldspar and quartz as such do not float with sodium oleate, but in practice selective flotation of beryl from feldspar and quartz in an ore is found to be impossible with sodium oleate as collector. A glance at the chemical analysis of typical beryl ore indicates the presence of several ions like Ca ++, Mg++, Al + + + and Fe+++ in abundance and Ti++++ and Mn++ in traces. Hence, in an attempt to explain the behaviour of feldspar in the beryl flotation, the effect of Ca++, Mg++, Al+++ and Fe+++, which are known as gangue mineral activators7'8 has been investigated. Materials and Methods: Lumps of beryl ore (hand picked) were boiled with 10% sodium hydroxide and washed with distilled water. They were further boiled many times with 10% hydrochloric acid till no positive test for iron was obtained with ammonium thio cyanate. This was followed by thorough flushing with double distilled water. The lumps were crushed in a porcelain mortar and pestle under water. The minus 65 + 100 mesh fraction was used for testing and was always stored under distilled water. Pure feldspar and quartz were similarly prepared and the minus 65 + 100 mesh fractions collected. Inorganic ions tried as activators were ca++, Mg++ , Fe++, Fe ++ and A1 +++ . Calcium nitrate, magnesium chloride, ferrous ammonium sulfate, ferric ammonium sulfate and aluminum nitrate of G.R.E. Merck grade were used. B.D.H. technical grade sodium oleate was used as a collector. The vacuumatic flotation technique developed by Schuhmann and Prakash was used for studying the effect of pH on flotability. 7 The indications given by this work were confirmed by using 10 g miniature cell.'

Jan 1, 1965

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By N. W. Lord

Having recently had occasion to make a series of analyses of fire-clays for the present Ohio Geological Survey, I found that the amounts of potash and soda determined indirectly by measuring the chlorides volumetrically did not " check " with those obtained directly. Investigation with the spectroscope showed the presence of lithia in what seemed very appreciable quantities. The examination was made of a considerable number of samples, and in every case this element was found, though in varying amounts, as judged by the intensity of the spectrum. To guard against error from the impurity of reagents, the whole process was repeated, using the same reagents in corresponding amounts, but leaving ont the clay. In no case did these " blanks" show lithia; hence the presence of this element in the clays seemed to be established conclusively. In the same series of analyses, titanic acid, in amounts varying from three-tenths to nearly two per cent., was found. The presence of titanium was first observed in the Ohio clays, nearly three years ago, in the examination of clays from Logan. The occurrence of this element is, of course, not unusual in clay, but I believe that none of the published analyses of Ohio clays give it; certainly none of the former Ohio geological reports speak of its presence. The following analyses show both the above ingredients. They were made during the summer of 1883.

Jan 1, 1884

By P. Datta, L. L. Handy

For a wetting phase displacing a nonwetting phase from a porous medium the distribution of the residual fluid may depend on displacement conditions. Although this subject has been debated in the literature, only a few experiments have been cited to support the various conclusions. Experimental results presented in this paper show that fluid distributions are dependent on imbibition pmcedures. Results agree qualitatively with predictions from the pore doublet model. If the rate of water imbibition is restricted, the nonwetting phase is trapped preferentially in .the larger pores as expected. But if the rate of water imbibition is unrestricted, trapping occurs somewhat more in the smaller pores. These conclusions were deduced primarily from relative permeability measurements. INTRODUCTION Relative permeabilities are known to depend on the saturation history of the porous medium. For either continuously increasing or continuously decreasing wetting phase saturations, however, they have normally been assumed to be single-valued functions of saturation. Severat investigators have compared relative permeabilities measured by different methods and have reported acceptable agreement.1-5 Studies of simple models of the displacement process suggest that the distribution of residual fluids can be influenced by the displacement method. If this is so, relative permeabilities also should depend on the method of displacement. These predictions have not been supported by experimental data. The object of this paper is to investigate experimentally some of the predictions of these model studies. The particular question of importance is whether steady-state and unsteady-state methods should be expected to give the same values of relative permeability. Much of the reported data showing agreement between steady-state and unsteady-state methods have been obtained on un consolidated sand. Johnson, Bossler and Naumann, however, compared steady-state and unsteady-state results for Weiler sandstone and found no significant differences.5 Levine made a detailed study of pressure and saturation distributions for a laboratory waterflood in a consolidated system but made no attempt to calculate performance from steady-state relative permeability data Bail and Marsden in a somewhat similar set of experiments did attempt a comparison of observations with predictions but the results were inconclusive.7 Excluding gravity, two forces affect the distribution of wetting and nonwetting phases during an unsteady-state, immiscible displacement: viscous and capillary forces. If relative permeabilities are indeed the same when measured by steady- or unsteady-state methods, the fluid distributions at the same fluid saturations must be similar for both methods. Furthermore, the implication is that the relation between capillary and viscous forces is the same for both methods insofar as the effect on microscopic fluid distributions is concerned. Unsteady-state displacements are normally run at high rates to maximize the ratio of the viscous to capillary forces. The objective is to reduce the effect of capillary forces on macroscopic fluid distributions. For floods in which the phase which wets the porous medium displaces the nonwetting phase, capillary forces compete with viscous forces in determining fluid distributions.8 The residual nonwetting phase is discontinuous. Competitive aspects of viscous and capillary forces and the resulting effect on water-oil distribution in porous media have been illustrated in an elementary way using a pore doublet model. This model and predictions from it have been discussed at considerable length by Rose and Witherspoon, Rose and Cleary and by Moore and Slobod.9-13 Rose and Witherspoon show that so long as water invades the model at a rate equal to or greater than the free imbibition rate, the water will move through the larger capillary of a doublet first and trap oil in the smaller capillary. On the other hand, if a negative pressure is applied to the water

Jan 1, 1967

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By Charles E. Wait

In the analysis of a set of interesting furnace-products belonging to the metallurgical cabinet of the School of Mines, I placed in the hands of one of my students a sample of litharge which gave the results quoted below. The collection of specimens from which this was taken, represents the products obtained in the blast-furnace treatment of argentiferous lead ores, also samples from the zinc process, and those from the cupellation of the enriched lead. The sample, when received, was marked "bismuth litharge," and was that obtained during the last stages of cupellation. It gave upon analysis the following : Per cent. Lead,.......85.36 Antimony,.......06 Bismuth ,........20 Copper,.....49 Iron,...... 69 Zinc,......18 Nickel,.....01 Silver,....2.94 Lime,.....36 Magnesia,....03 Silica,.....12 Sulphuric anhydride,. .32 Carbonic anhydride,. 1.25 Water,.....24 Oxygen,..,.7.80 99.95 At present I wish merely to call attention to the large percetage of silver present (equal to 857 ounces Troy per ton of 2000 pounds avoirdupois), and also to note two or three determinations that I have recently made, with a view to ascertain, if possible, the condition in which this silver exists. If I mistake not, it is usually assumed that silver exists in litharge in the metallic state; and it is, indeed, in the analyses of litharge, rarely expressed otherwise. This method of reporting the silver is, no doubt, due to the accepted statements that the oxides of silver are reduced to the metallic state at a temperature of 300' C. or less. The following experiments lead me to believe that silver exists in litharge, not entirely in the metallic state :

Jan 1, 1887

By Louis D. Huntoon

After the completion, in 1905, of the Hammond Mining and Metallurgical Laboratory of the Sheffield Scientific School, Yale University, it became necessary to secure and assay a large assortment of ore-samples, and to arrange the results in such a manner as to admit of use with the least amount of work on the part of the instructor. At first, pulp-samples, together with their respective assays, were secured from the mines, smelters, and public aesayers, but this practice did not prove satisfactory. It was not only difficult to secure a suffciently large supply of material, but it was also impossible to secure the proper assortment required for instructing students. It involved considerable work for the donors to select the samples and furnish a record of the assays, and also for the instructors to examine each pulp and determine its character. Some of the samples did not contain a sufficient quantity of pulp for the student to check his work in case his first assay did not correspond to the record. In order to increase the number of samples and to vary the character of the material, pulp-samples were later mixed with barren rock and with sulphides, but this method also was unsatisfactory and has been discontinued. At present, small lots of ore are secured by gift or purchase from engineers, public assayers, and the managers of mines, mills, and smelters. These lots weigh from 10 to 100 lb. each, and are rarely finer than 0.25 in. in size. The larger samples permit of a careful study by the instructor in order to determine the best method of assaying to be followed. In universities in which assaying is taught the record of the samples should fulfill the following requirements:

Jan 1, 1910

By J. W. Gwinn

THE underground haulage system in the lead-silver mine of the-Bunker Hill & Sullivan Co., situated at Kellogg, Idaho, is the most extensive in the Coeur d'Alène district, comprising about 35,000 ft. of tunnels, drifts, and cross-cuts where locomotive haulage is in use. The main working adit, known as the Kellogg tunnel, or No. 9 level, is approximately 10,000 ft. in length from the portal to the main working shaft and extends beyond that about 4,500 ft. in each of two directions. On this level all the ore from the Bunker Hill & Sullivan, the Sierra Nevada Consolidated, and the Caledonia Mining Co. an average of 44,600 tons per month-is hauled to the mills, located a short distance from the portal. Electric haulage by the trolley-type locomotive is used on this level throughout. Below this level, at intervals of 200 ft. vertically, are five other working levels (Nos. 10, 11, 12, 13, and 14); and the total haulage distance on these, where electric locomotives are used, is approximately 16,000 ft. No. 13 level has but recently been opened up and is not working-to capacity; while the main cross-cut on No. 14 has just been started, and has no need of power haulage. Of the four levels equipped with electric haulage, Nos. 11, 12, and 13 have storage-battery locomotives, and No. 10 still retains the trolley type by reason of the small and decreasing tonnage produced.

Jan 2, 1915

By George L. Heath

This paper is devoted chiefly to the coal-fields of the western part of the province of Chili and the eastern part of the province of Shansi; but the outline of this belt will give some idea of the extension of the coal-fields over northeastern China. This part of China is topographically divided into: (1) the mountainous peninsula of eastern Shantung; (2) the coastal plains, extending W. and SW. from the gulf of Pechili; and (3) the mountains and table-lands N. and W. of the coastal plains. The plains extend N. and W. from the gulf to within from 10 to 25 miles of the Great Wall, while their SW. extension covers western Shantung and reaches W. along the Yellow river almost to the southern boundary of Shansi. A line joining the mapped coal-fields, shown in Fig. 1, almost gives the western boundary of the plains; since these areas lie on the border of the plains—except the Tsê Chou field, which is on the table-land, 20 to 25 miles from that border. The coal-fields which have been mapped and investigated by the author are shown in Fig. 1. The one at and around Tongshan is known as the K'ai-p'ing coal-field; the one W. of Peking has been called the Wang-p'ing coal-basin; the one SW. of Pao-ting and N. of Chêng-ting may be called the Lingshan coal-field; and the one at and around Tsê Chou is known as the Tsê Chou coal-field. I. The K'ai-p'ing Coal-Field. As is shown in Fig. 2, most of this field lies in the coastal plains, and is therefore covered by alluvium and loess, which have buried the older rock-beds, and the more gentle and older topographic outlines, to such an extent that most of the re-

Jan 1, 1902

By Albert F. J. Bordeaux

The immediate vicinity of the sea-shore, affording special facility for the exportation of ores, makes it possible to work certain mines in the Vladivostok district, which, in more remote places of Siberia., would remain unproductive. Outside of the city of Vladivostok the population is small and the country is very little prospected. Additional discoveries of valuable deposits like the large body of calamine which has recently been opened in the neighborhood of earlier worked lead-silver ores, in the Tetiuhe valley, are still in the field of possibilities. For many years gold alone was produced, in part from the coastal rivers and in part from a quartz-vein on Askold island near Vladivostok. But the production is diminishing, and prospectors are looking for other rivers in the interior, such as the tributaries of the Ussuri. These rivers are now more accessible than formerly, due to the slow but gradual development of colonization by the Russian peasants. The few natives of the country, called Orodjones, are of the Chinese race. They resemble the North American Indian and are hardy fur-hunters. They have given some attention to placers and have already shown good specimens of gold-dust from the rivers Iman, Bikin, Noto, etc. Coal-mining was begun in the Vladivostok region more than 20 years ago, but in a somewhat irregular way. The industry is not as yet important and the best coal-seams are badly prospected, or are even neglected. Copper, lead, and iron exist in several places. The amounts give some encouragement to the anticipation that the discoveries will give rise to important metallurgical works. I here present a review of the various deposits, based upon such safe information as is in hand, when I have not drawn upon my personal observations. Fig. 1 is a map of Eastern Siberia, showing the mineral deposits.

Jan 1, 1913

By H. C. van Elst

Ultrahigh-speedphotographic and electronic meth-ods were applied to an investigation of details of brittle-fracture propagation in steel. The brittle fractures studied were obtained in steel plate with the aid of a Robertson apparatus. It was found that a brittle fracture proceeds by discrete steps ranging from 30 mm near the stop temperature to less than 2 mm at lower temperatures. The halting FROM prior metallographic observations of brittle fracture in steel' it could be concluded that the distribution of mechanical twins along a brittle fracture was similar to the distribution of mechanical twins induced by explosive deformation. It was therefore assumed that a running brittle fracture created stress waves, cf. Refs. 2-7. An emission of stress waves by a brittle fracture, however, seems only conceivable if the fracture propagates by discrete steps. For this reason a study of the details of times between successive steps drop in this tem-perature region from 20 usec to about 1 psec. The stepwise propagation mechanism is accompanied by an intermittent emission of stress waves of the order of 100 to 200 kg per sq mm. These stress waves seen1 to play an important role in the mechanism of brittle fracture as will be discussed. brittle-fracture propagation was undertaken to investigate the possible determination of the fracture steps and the emitted stress waves associated with the assumed mechanism. The more practical object of this work is the development of a test method for the determination of the ductile-brittle transition in small specimens. This has special advantages for the study of irradiation damage in steel. In this test method, which will be published in a following paper, the stress waves emitted by an actual brittle fracture are reproduced with explosive or electrical means and are then transmitted through small specimens at various temperatures. In the present paper only the results of the brittle-fracture study will be reported.

Jan 1, 1964

By G. S. Brooks

The tendency of the oxides of such metals as aluminum, zinc, chromium, and calcium to form compounds at high tempera tures with iron oxide is well established by past investigation. Data of this reaction, as developed in laboratory research, have been contributed by Burleigh, Hofman, and Wells, in America, and by many others abroad. A partial bibliography of the subject is appended. From these authorities we learn that the ferric oxide here has the function of an acid, giving in the case of ZnO a zinc ferrite, with a normal composition of ZnOFe2O3 This formation of zinc ferrite particularly affects the success of such processes as leaching or magnetic separation, and thus becomes practically important to the metallurgist. But the meager existing data do not entirely agree; and quantitative results from muffle-practice are conspicuously absent. Furthermore, it being of some general importance to the zinc smelter in both roasting and reduction, the following few notes of operations oil a commercial scale are contributed: I. Physical Properties of Zinc Ferrite. As formed for the most part synthetically by investigators, zinc ferrite exhibits characteristic physical properties, such as octahedral crystals, dark color, and a density over 5, together with a slight magnetic attractability. In examining with the microscope many products of mechanical muffle-roasting kilns, it is, however, impossible to find individual grains which can be identified as consisting entirely of zinc ferrite. The variety of colors, especially where each grain of blende was mechanically free from marcasite, rather conveys the impression of a partial ferritization of the grain. One side or end, for example, may often have the hard, dense surface and dark red to black color of the ferrite, while the balance shows the usual light yellowish brown of a normal iron-free blende.

Jan 1, 1914

By Christopher W. Schram, Allan B. Tanner, Frank E. Senftle, George R. Boynton, Philip W. Philbin

Abstract-A borehole sonde wing a 252Cf neutron source and a Ge(Li) gamma-ray detector was field tested in a coal bed in Belmont County, Ohio, to ascertain whether such a device could be useful as a coal-exploration tool. As the sonde was lowered into the borehole, successive spectra were accumulated over short time intervals. The intensities of the capture gamma rays from hydrogen and of decay gamma rays from aluminum were determined simultaneously in each spectrum. A log of the intensities versus depth shows the depth and thickness of the coal bed.

Jan 6, 1978

By William A. Vogely

Mining employment in the United States declined from 986,000 employees in 1948 to about 600,000 employees today. This has occurred even though the Index of Physical Volume of Mineral Production (1957-59=100) has increased from 88 to 111 and the value of mineral production measured in constant(1957-59) dollars has increased from $14.7 billion to approximately $19.3 billion. Average unit mine value has increased 24% as compared with a 34% increase in prices in general. Apparent consumption has increased more than domestic production, indicating an increased dependence on imports. The mineral economy presents a complex pattern of development factors in the post-war period. This article presents a technique by which the various forces that have been acting on the market for a mineral commodity may be sorted out and by which the extent of the impact of technological change in use as well as the technological change in production can be measured. If one is interested in delineating fully and completely the impact of technological change upon the mining industries, it is not sufficient to describe the increase in productivity reflected by the above employment and production figures. What is reflected there is only the effect of technological change in the production function of the commodities under concern. These effects are obviously very substantial and have major implications for labor, capital and supplying industries. However, they are not the only effects of technological change and, in fact, may be relatively minor when the impact which arises because of changing technology in the using or consuming industries is considered.

Jan 4, 1965

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By R. A. Swalin

IN this paper, the results of an investigation concerning the diffusion of three elements, magnesium, silicon, and molybdenum, in nickel are presented. The work represents a continuation of a diffusion program relating to solute diffusion in nickel. The program has the dual aim of obtaining useful diffusion data and of yielding insight into the factors governing solute diffusion in close-packed metals. The first paper of this series has been published earlier? In both investigations, in agreement with recent results from other laboratories, the activation energies for solute diffusion were found to be close but not identical to that of self-diffusion in the pure solvent in question. In order to obtain valid diffusion data, certain experimental pitfalls recognized only in recent years had to be avoided. Chief among these were the necessity for minimizing short-circuiting diffusion paths such as grain boundaries and the necessity for using low solute concentration gradients. In this series of investigations the following precautions were taken in an attempt to minimize such errors. 1) Samples with large grain sizes, 0.5 to 10 mm, were prepared. 2) The diffusion coefficients were measured at relatively high temperatures, since imperfections such as dislocations play a less important role at such temperatures than at lower temperatures. 3) Alloys containing less than 1 atomic pct were chosen for study. Experimental Work Materials—A diffusion couple technique was employed in the experimental investigation. Briefly, this technique consisted of the following. A diffusion couple was fabricated by placing a flat face of a cylindrically shaped alloy disk against a similar face of a pure nickel disk, and a bond was formed at an intermediate temperature under pressure. The diffusion couple thus fabricated was subjected to a diffusion anneal at higher temperatures for a measured period of time and then sectioned perpendicular to the direction of diffusion. After analyzing the sections for solute concentration the diffusion coefficient was determined from a probability, plot of concentration vs distance from the diffusion interface. Vacuum melted Mond nickel was used in the experimental program. The chemical analysis of this nickel is listed in Table I. Alloys used were prepared

Jan 1, 1958