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By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By J. C. Bartlett

The following discussion was suggested by an experiment of Mr. Krom, the Manufacturer of air-jigs, to illustrate the superiority of air over water as a medium of concentration. The paper is written in the interest of no system of concentration, but simply to test the experiment, and, perchance, to add something to the general fund of information on the subject. To speak of testing an experiment by a theoretical discussion, may seem a misuse of terms, but the theories concerning falling bodies and the resistance of fluids are pretty well crystallized into laws, which may properly be used to show where experiments which seem to refute them were improperly performed, and that instead of refuting they only corroborate. It is well known that a sphere of galena & inch in diameter, and a sphere of quartz 1/2 inch in diameter, are equal falling in water ; that is, these two spheres, being placed together in a column of water at rest or in motion, will practically remain together, filling or rising together, or remaining in suspension. Mr. Krom, to show that these

Jan 1, 1879

By F. O. Jones

The capabilities of small proportions of divalent cations, such as calcium or magnesium, for controlling clay blocking are reported. Potentially sensitive formations can be exposed to fresh water if at least one-tenth of the salts dissolved in both the native water and invading fresh water are calcium and magnesium salts. Often, even less suffices. The behavior evidently depends upon the cation exchange properties of the clays, which favor adsorption of calcium and magnesium over sodium. Clays having sufficient adsorbed calcium and magnesium resist dispersion by water and consequent blocking of permeability. An allied phenomenon, the dependency of clay blocking on salinity contrast, is also reported. Abrupt change from highly saline to fresh water can cause blocking which may not occur if salinity is lowered slowly. A process related to osmosis is thought responsible for this behavior. Applications of findings to drilling, fracturing and water flooding are discussed. INTRODUCTION Many formations, when exposed to fresh water, can lose permeability through clay effects.',' For example, drilling-mud filtrate can cause oil permeability decreases, which persist long enough to interfere with drill-stem testing and well completion.3 Ultimate productivity may suffer when clay damage is severe, especially if drawdown pressures are low.' The injection pressures and the time required for water flooding can increase if clay blocking occurs. Earlier work indicates that clay blocking is caused by obstruction of flow channels by clays or other mineral fines dispersed by fresh water.'!" It is well known that increasing salt concentrations in water tends to prevent clay blocking. Also it is well established, although perhaps not as widely known, that the nature of the dissolved solids is also important. If, for instance, formation clays are exposed to calcium chloride solution and then exposed to weaker solutions of calcium chloride or distilled water, considerably less permeability damage results than if the clays had been exposed instead to sodium chloride solutions. The reasons for this behavior are: (1) clays are cation-exchange, or base-exchange, materials similar in this respect to zeolites or exchange resins, and (2) clays in the calcium form do not disperse easily in fresh water, whereas clays in the sodium form do. The base-exchange form of a clay is easily altered by flowing a solution through it. For example, a sodium clay can be changed to a calcium clay simply by passing a calcium chloride solution through the clay bed. There is general agreement that the reason calcium and magnesium clays do not disperse easily in fresh water is because the calcium ions do not ionize easily from the clay surfaces.' Sodium clays, however, are believed to allow the sodium ions to ionize from the clay particle surfaces. In fresh water, this allows the particle to accumulate a net negative electrical charge great enough for the particles to repel one another and, therefore, disperse more easily. The foregoing suggests that, even in the presence of a large excess of sodium, a relatively small ratio of divalent cation, such as calcium or magnesium, might serve to prevent clay dispersion. The divalent ion probably adsorbs to a disproportionately large extent, because of being adsorbed more tightly, with the result that the proportion of divalent cation on the exchange positions of the clay might then be great enough for the clays to resist dispersion. Consequently, an investigation was conducted to find how mixtures of salts in solution influence clay blocking. APPARATUS AND PROCEDURE Water permeability tests were conducted using conventional techniques. The equipment is illustrated schematically in Fig. 1. Flow rates of solutions driven through small core samples at known temperatures and pressures were measured. Regulated compressed air, usually at 10 to 15 psig, was used to drive the solutions. Core samples 0.75 in. in diameter and 1 in. long were used for the most part. Cores were saturated by evacuating and then admitting a de-aerated solution. Tight core samples were first saturated with carbon dioxide gas and then evacuated and saturated with the test solution. After saturation, 140 psig pressure was imposed for several hours. Cores were tested to insure absence of gas saturation by a Boyle's

Jan 1, 1965

By F. Clerf

Blast-furnace practice in France is determined more or less by the character of the ores used. Some French ores are siliceous and others are calcareous, therefore by proper burdening a self-fluxing mix can be used. This is not always done, as, for instance, at the Caen furnaces of the Société Métallurgique de Normandie, where the Soumont ore of Normandy is used, which is a carbonate. This ore is crushed and calcined at the mines, yielding a product that is porous and well sized for blast-furnace consumption. The lines of the Caen furnaces are given in Fig. 1. Originally these furnaces had 16 tuyeres; six are plucked and these tuyeres are set in the lower part of the bosh. Operating data on these furnaces are given in Table 1. Table 1.—Operating Data, Caen Furnaces Kg. Lb. Blast-furnace burden per ton of iron: Soumont ore....................................... 200&2100 (44004650) Limestone...................................... 900-1000 (2000-2200) Basic Bessemer slag (bearing phosphorus).............. 100 (220) Scale.............................................. 35 (77) Manganese ores.................................... Coke.............................................. 1100-1200 (2420-2640) Coke analysis: Ash, per cent............. 9.5 H2O, per cent............. 4.0-10.0 Flue dust (approx.), kg. per metric ton.... 200 (440 lb.) Blast volume, cu. m. per hr.............. 83,000 (49,000 cu. ft. per min.) Preesure, lb............................ 12 Blast heat, deg. C....................... 650 (1200" F.) Top temperature, deg. C................ 250 (445O F.) Top-gas analysis, per cent............... CO2 9.3 CO 30.3 O2 0.3 H2 3.0 Production per 24 hr. about 510 tons. MINETTE ORES The most important ore deposits in France are in the west of Lorraine. They are called the "minette" ores and are of two classes-—siliceous and

Jan 1, 1937

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.' Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965

ADVANTAGES OF LIFE MEMBERSHIP The Institute calls the attention of members to the following advantages of obtaining life membership: 1. One payment avoids the trouble of future payments. 2. The interest on $150 is less than the annual dues. 3. Provision is thus made early in life for the less productive years. 4. In case of in increase of clues at any time in the future life members are exempt from increased payments. Excerpt from, By-Laws. Article III. Section 3 Any Member or Associate not in arrears may become, by the payment of one hundred and fifty dollars at one time, a Life Member or Life Associate, and shall not be liable thereafter to pay annual dues. The money thus received shall be invested and only the income thereof used for current expenses of the Institute.

Jan 1, 1916

US 4,192,851-Recovery of elemental sulfur and the metal values from a complex sulfide ore containing two or more of the metals zinc, lead, copper, silver, gold and/or other metals. A mixture of ore and sulfuric acid and/or spent electrolyte is flowed at optimum temperature and pressure in a quiescent zone to dissolve selected metals and sulfur and coalesce the sulfur. The coalesced sulfur and unreacted sulfides are separated by flowing the leach slurry with an upward velocity component The separated materials are discharged and further processed by conventional methods as war- ranted. H.E. Hirsch, J F. Higginson, EG. Parker, and G M Swinkels, assigned to Sherritt Gordon Mines Ltd. Mar. 11, 1980. 6 pp. (423-28) Filed. 3-14-78 (886,368). Priority. United Kingdom, 3-15-77 (10800/77).

Jan 1, 1982

By J. J. Marcus

Mineral industry decision-makers are frequently required to select between competing equipment. Various criteria and methods are currently being used, and this writer would like to suggest a method recently tested on two large power shovels in an open pit mine. An initial examination of both shovel A and shovel B indicated that the latter should give the best overall results. since: 1) It swings 13% faster; 2) it carries a dipper with 23%: greater capacity; 3) purchase price is 8.6% lower; 4) shovel weight is 12.5% greater; 5) it has considerably greater bail pull under most operating conditions; 6) the electric controls are of a more modern design. However, shovel B has half the service life. With these points in mind, shovel A was selected by The Buckingham Method, an operations research technique.

Jan 9, 1965

By Charles M. Bayer

Reading in the AIME annual reports that certain activities have been financed by the Rocky Mountain Club Fund, less senior members of the Institute may wonder. "What's the Rocky Mountain Club?" Less youthful members will not have to wonder. They will recall the Club as an intriguing, almost fantastic organization, largely of western mining men, that flared across the New York horizon, flamed brilliantly for a little more than two decades, then sputtered out of existence- glorious even in its last flash. It was the only product of its mold, a fabulous group of magnanimous men who unhesitatingly sacrificed a cherished dream for which they had raised millions of dollars so that the money, instead of creating a magnificent club house, could be used instead to save the lives of starving Belgian children in World War I.

Jan 12, 1964

By Irvin Mayes, Maher E. Tadros

The effects of particle properties and dispersion on the filtration behavior of magnesiumhydroxide, silica, and polystyrene suspensions in aqueous media were examined. It was found that effective separation of particles can be achieved using filter media with larger pore diameters than the size of the particles. The addition of electrolytes, at concentrations lower than the critical coagulation concentration, to suspensions of polystyrene or silica resulted in an increase of the cake resistance. This result was interpreted in terms of a decrease in the effective particle size due to the increase in ionic strength. For magnesium hydroxide, an increase in the absolute value of the surface charge was associated with an increase in cake resistance and a decrease in cake compressibility. Low cake resistance values were obtained with suspensions of large particles with low surface charge and blocky morphology.

Jan 1, 1980

By Harrison Schmitt

THE definitions of the terms commonly used in connection with metamorphism at elevated temperature near igneous contacts are re-examined. As the study of tactite zones associated with igneous contacts progresses, more and more emphasis is put on the localization of the ore by structural forms. The generally early age of the silicates and late age of the sulphides is well established. Postsilicate structural deformation is likely to localize ore bodies. The silicates are often replaced by the ore minerals. We may not be far from proving that the elements involved in the formation of silicate aureoles are merely normal "volcanic" emanations, that silica, lime, magnesia, and alumina and probably soda and potash are likely to undergo local transfers only. The work of Newhouse suggests the agents of the formation of sulphides in deposits of various classifications are the volcanic emanations.

Jan 1, 1947

By A. J. W. Headlee

RECENT interest in germanium centers around its use as a semi-conductor of electricity in electronic devices. It is generally believed that germanium transistors, diodes, triodes, photocells, and rectifiers will largely replace the present-day vacuum tubes. The germanium electronic devices are much smaller, lighter, and more resistant to shock, and they require only a small fraction of current required for conventional devices. Hence only a small amount of heat is given off by the equipment. This development will require many times the quantity of germanium now being produced, which in 1948 was approximately 1000 lb1 and was obtained almost entirely from zinc ores in Missouri, Kansas, and Oklahoma. No one knows with certainty what the demand will be for germanium by 1956. It may be 40,000 lb.1 Known concentrations in zinc ores are not sufficient to

Jan 10, 1953

By Eugene P. Pfleider

RECENT interest in germanium centers around its use as a semi-conductor of electricity in electronic devices. It is generally believed that germanium transistors, diodes, triodes, photocells, and rectifiers will largely replace the present-day vacuum tubes. The germanium electronic devices are much smaller, lighter, and more resistant to shock, and they require only a small fraction of current required for conventional devices. Hence only a small amount of heat is given off by the equipment. This development will require many times the quantity of germanium now being produced, which in 1948 was approximately 1000 lb' and was obtained almost entirely from zinc ores in Missouri, Kansas, and Oklahoma. No one knows with certainty what the demand will be for ger-manium by 1956. It may be 40,000 lb.1 Known concentrations in zinc ores are not sufficient to

Jan 1, 1954

By S. V. Krishnan, I. Iwasaki

In the upgrading of finely disseminated iron ores, selective desliming is the critical step that must be controlled to achieve efficient flotation. A prerequisite for selective desliming is a properly-dispersed pulp; sodium silicate is commonly used as a dispersant. The mechanism by which sodium silicate acts as a dispersant in the presence of calcium ions was examined by streaming potential measurements, settling tests, abstraction density determinations, selective flocculation tests, and scanning electron microscope observations. The study established that calcium silicate precipitates on the mineral surfaces dispersed the pulp. Although sodium silicate was a nonselective dispersant, the addition of corn starch aided flocculation of goethite over quartz at low silicate additions, but became ineffective at higher silicate levels. A model is presented to explain the dispersant mechanism of sodium silicate in the presence of calcium ion for selective flocculation of iron ores.

Jan 1, 1983

By John V. Beall

THIS is not simply the story of how a water filled shaft was developed into a million-ton- a-year producing mine in the space of four critical years, although it is reason enough for telling it, but it is also the saga of an engineering achievement in which knowledge nurtured by years of experience in coal and ore mines was blended together and the best from each type of mining selected. The entire system of mining was detailed on maps by the mining engineering department before the shaft was unwatered, and subsequent development followed these plans nearly to perfection. The selection of machinery was particularly critical as it was necessary to push production from only a few headings in the early stages of development and metal mine machinery was being used in a coal panel-system of mining.

Jan 12, 1950

By Charles T. Holland, David A. Olsen

Considerable work has resulted in the development of a formula by which the strength of coal pillars for an L to T ratio of up to 12 may be estimated. One of the factors involved in this formula is the coefficient of friction between the coal pillar and the adjacent rock with which it is in contact. This paper presents the results of studies on sandstone, limestone, shale and coal and the coefficient of friction between coal and the other three under wet and dry conditions. With the coefficients of friction thus determined and the use of results obtained earlier by Meikle and Holland, it seems probable that coal pillar strength may be more closely estimated. Several investigators1-3 have found that the com-pressive strength of cubical coal specimens can be correlated by an equation such as

Jan 1, 1969

By Leonard Grimshaw

DIFFUSION Of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been consider-able, and includes many reports in foreign languages. This work has recently been well reviewed by Mehl1 and Krynitsky,2 and the reader is referred to their excellent bibliographies.

Jan 1, 1937

By Edward S. Cook

For several years past, dating particularly from the days of serious "ore-dirt" complications at the Warwick furnace, I have been desirous of providing some safe, quick and easy method of relieving the tuyeres of slag, when the cinder- and iron-notches are chilled through loss of heat in the clucible or when, from dropping or jumping of stock, the molten slag is forcibly driven into the bellyand leg-pipes. Various methods were proposed, but objections of one kind or another always presented themselves, and the subject was postponed to a more convenient season. In the summer of 1887, while running on anthracite alone, 1 found the various expedients in use to be so utterly valueless, that the importance of a practicable tuyere slagging-valve impressed me more forcibly than ever. The holes left in the cast-iron jacket at one side of the bottom of the water-blocks were found to be of no value whatever. The swinging or hinged cap on the elbow of the belly-pipe, while convenient to permit the removal of lag after the belly-pipe was partially or wholly filled, could not be adapted to discharge the slag before solidifying, except at great risk to the men and loss of time just when the constant running of the engine and the keeping of blast on the furnace was of the utmost importance. By removing keys from the caps and holding them in place with props, the slag could be discharged through the tuyeres and belly-pipes, with the engine running, by knocking the props away at a given signal. This method is extremely hazardous to life and limb, and I have always hesitated to make use of it. When the furnace is in such condition as to require the adoption of some method of the kind, the stoppage of the engine, cooling the blast and the contents of the crucible, always aggravates the trouble. When the caps are blown open and the slag is discharged by removal of the props, it is necessary to stop the engine to replace them. An hour or more will elapse before this can be done, as the slag must be partly removed before the tuyeres can be approached by ordinary mortals, and the caps handled and fastened in place again. Any movement of the stock is liable to burn the workman, as he stands, securing the cap in front or at one side of the open belly-pipe.

Jan 1, 1889

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By T. E. Leontis, R. S. Busk

WORK was initiated several years ago at The Dow Chemical Company to determine the applicability of powder metallurgy processes to magnesium and its alloys. Although it was found possible to apply the normal techniques of compacting and sintering, it was discovered early that the technique of extrusion offered special promise. This technique and the alloys produced were therefore studied extensively, and the present paper is a partial report of those studies. It is expected that a second paper will discuss more extensively some of the alloy systems simply mentioned here. Although the literature on powder metallurgy is very extensive, there are only two articles dealing with magnesium13,14 and there is no reference to the direct extrusion of the powder of any metal without the preliminary step of compacting. Furthermore, no mention has been made of the possibility of designing alloys by the technique of powder extrusion, particularly alloys that cannot be made in any other way. Sauerwaldl3 discusses the extrusion of magnesium and aluminum powder to produce alloys containing nonequilibrium phases, but again he emphasizes the importance of pre-compacting before extrusion. There seems to be general agreement that some form of hot-pressing is essential to obtain in a compact the full theoretical density of the metal used.'-" The nearest approach to the technique of direct powder extrusion is that of extrusion of pre-sintered compacts,'-" for which the best review through 1944 is that by Kieffer and Hotop.11 Ensign* discussed a specialized technique of "extruding" already compacted and sintered gears for the purpose of sizing. Sauerwa1d13 discussed the compacting and extrusion of magnesium and magnesium-aluminum alloy band-saw chips. The properties of the extruded compacts were found to be comparable with those of extrusions prepared from solid billets. He also extruded a compacted mixture of magnesium and aluminum powder and found the properties to be somewhat different from those obtained on an extrusion made from a cast billet of the same composition. The second reference dealing specifically with the powder metallurgy of magnesium is Stern's patent," in which is described the extrusion of scrap chips and turnings following a hot-pressing and sintering step. Considerable emphasis in most of these articles is placed on the necessity of atmospheric protection to minimize the danger of oxidation. Experimental Procedure The first experiments were made with the small extrusion press shown in fig. 1. With this press, billets of about 1/2 in. diam are used to produce wire

Jan 1, 1951