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By D. C. McLean

This report summarizes the work that has been done during the past several years in adapting resins for use as auxiliaries in mine roof support. The resins were applied in two ways: 1) by injection into the strata, and 2) as a bonding agent for roof bolts and reinforcing bar. The Explosives and Mining Chemicals Department of the American Cyanamid Co. has worked during this period in cooperation with the Roof Control Research Group of the U.S. Bureau of Mines, the Pattin Manufacturing Co., the J. H. Fletcher Co., the Homestake Mining Co., the U.S. Steel Corp., the National Mines Corp. and the Pocahontas Land Corp. in an effort to create resin formulations and methods for applying them as a practical and sate type of roof support for mining areas particularly where conventional support is inadequate, yet expensive. This, work has involved much pioneering in a field where theory, speculation, and pure mythology predominates, and little basic engineering data is available. It is strange butt true that, despite the importance of roof control both from an operational and safely standpoint, there is scarcely a mining' company in this country that has an engineer, or anyone, assigned to the study of roof support problem, except temporarily--after a bad roof fall. The responsibility for improving roof control methods seems to have been placed entirely upon the shoulder, of the USBM, various State departments of mines, and individual roof bolt manufacturing; companies. It was in cooperation with the USBM that Cyanamid first developed resins for mining use.

Jan 1, 1964

By E. H. Snow, B. E. Deal

Instability effects in semicanductor devices have long been attributed to the motion of charges on or within oxide layers on the surface. These effects are of critical importance in metal-insulator-semiconductor MIS) field-effect devices. For this reason, the capacitance-voltage or the conductance-voltage characteristic of these devices can be used as a sensitive detector to study charge transport and polarization effects in the oxide or insulator. A review is given of the results of such studies of thermally grown SiO2 as well as of other insulating films of importance in silicon technology. Three types of effects are distinguished. The first of these is the drift of mobile cations within the dielectric, examples being thermally grown SiO, which is often contaminated with sodium ions, and a variety of other glasses in which the mobile ions are a part of the glass composition. The second effect is a dipole-type polarization which occurs in phosphosilicate glass films obtained by reacting P2O5 with thermally grown SiO2. The third effect involves the transfer of charges between the dielectric and the silicon electrode. This occurs in silicon nitride and other deposited dielectrics. It is concluded that MIS studies have provided a powerful technique joy the study of charge transport and polarization effects in insulating films. The knowledge gained from these studies has led to an understanding of surface effects on conventional transistors and diodes as well as making possible stable MIS transistors. THE metal-insulator-semiconductor field-effect transistor is conceptually the oldest type of active semiconductor device.' The earliest attempts at making this device were frustrated because of high surface state densities at the interface between the semiconductor and the gate insulation.' However, by using a silicon substrate with thermally produced silicon dioxide as the gate insulation, this problem was solved and metal-silicon dioxide-silicon devices with good characteristics were made as early as 1960. 3 Yet it was still over 5 years before these devices became a commercial reality. This delay was largly due, not to surface states, but to stability problems associated with polarization effects within the insulating layer which caused the threshold voltage of the device to drift under temperature and bias treatments. The solution to these problems has not only made possible stable MIS devices, but it has added immensely to our understanding of failure mechanisms in conventional bipolar transistors and has added to the reliability of ali types of planar devices. In this review, we shall first describe the effects of various types of polarization phenomena on MIS device characteristics. Then, since thermally grown SiO, is by far the most important insulator used in these devices, we shall review historically the type of instabilities which have been observed in thermal oxides, the attempts at understanding and eliminating them, and the present status of the problem. We shall then turn our attention to the various deposited insulators which have been used, including lead glasses, phosphosilicate glass, vapor-deposited silicon oxide, and silicon nitride. Interestingly enough, many of these materials show polarization effects which are quite different from those generally observed in thermally grown SiO2. THE EFFECTS OF POLARIZATION PHENOMENA ON MIS CHARACTERISTICS The simplest MIS device and the one which has been most frequently used in the study of polarization effects is the MIS capacitor. Two modifications of this structure with single- and double-layer dielectrics are illustrated in Figs. l(a) and (b), respectively. The capacitance of this structure as a function of voltage applied to the metal gate electrode is plotted in Fig. 2 for the case of an n-type silicon substrate. When the silicon surface is accumulated (positive bias) the measured capacitance is just that of the insulating layer C. When the surface is inverted (negative bias), the capacitance is that of the insulator and a silicon depletion layer in series CoCs/(Co + Cs). Indicated on the horizontal axis of Fig. 2 is the voltage VT at which the silicon surface becomes strongly inverted. This voltage corresponds to the threshold or turn-on

Jan 1, 1969

To THE BOARD OF DIRECTORS AND MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS. GENTLEMEN Like every other significant activity in the United States today, the work of the Institute has been affected by and adjusted to the prosecution of war against Germany, .Japan and their satellites. As the elaborate engines and materiel of modern mobile warfare are made, for the most part, of metals and other minerals; and are powered by mineral fuels, the industries -represented by the A.I.M.E. are of primary and vital importance. Of some 29 critical materials officially listed by the War Production Board, 24 are minerals. An alternate for one of the others, rated as a nonmineral, is to be made principally from petroleum. This alludes, of course, to rubber. The procurement of tremendous quantities of such raw materials and the effective processing, fabrication, and utilization of them depend on members of those branches of the engineering profession represented by the A.I.M.E.

Jan 1, 1943

Institute of Metals Division Iron and Steel Division Extractive Metallurgy Division Council J H Scaff (IMD) Chairman, Robert W Shearman, Secretary, J S Smart, (IMD), P T Stroup, (EMD), A W Schlechten, (EMD), J S Marsh, (ISD), A W Thornton, (ISD), M E Violin, (MED), D S Eppelsheimer, (MIED) Journal of Metals Editorial Advisory Committee J S Smart, Jr, Chairman, W A Dean, J C Kinnear, Jr, T D Jones, Evan Just, John Marsh, M Tenenbaum Pacific Northwest Regional Conference A Y Bethune, General Chairman, Frank N Marr, Chairman, General Arrangements, R J Lapee, Chairman, C P Love, (EMD Program), W M Armstrong, Chairman, Physical Metallurgy Program, L W Heinzinger, Chairman (ISD Program), J P Spielman, Chairman, (MIED Program) New England Regional Conference K H Mairs, Chairman, W A Backofen, Vice-Chair¬man, Delmar E Trout, Secretary, G W Coleman, Treasurer, F H Wilson, Past Chairman, Members at Large Sidney Siegel, Boston, G F Donahue, Connecti¬cut Representatives from Connecticut Frank Chudy, J E Chafey Representa¬tives from Boston N L Reed, E Gordon

Jan 1, 1955

By J. H. Fletcher, S. M. Cassidy

Air has been cooled, heated, washed, humidified and dehumidified for many purposes and in many industries. At a number of metal mines air is conditioned to reduce the high humidity and unbearable heat found in deep workings, and at some mines air is washed to allay siliceous dust. Steam is introduced into the intake air at many coal mines, particularly in winter, for the purpose of keeping loose coal dust so moistened that the hazard of an explosion is lessened. This paper will describe a further successful application of air conditioning in a coal mine, where, for over three years, all intake air has been cooled to a constant temperature for the sole purpose of preventing roof falls. Effect of Warm Weather on Mine Roof It is generally known by mining men that some, if not all, coal mines have more trouble from bad roof during the warm summer months than in winter. Also, it has been observed that roof on intake airways is usually worse than on the return entries, after the air has circulated through the mine. Some mines and some coal seams are much more affected than others. In the Clinton district of Indiana, the No. IV coal seam has a good, firm, gray shale roof except during the summer months, when it deteriorates badly and falls in small slabs 1 to 6 in. thick. Timbering is not very efficacious during this period because in time the roof will shear around the supporting prop or crossbar and either dislodge the timber or leave it supporting only a few inches of crumbly shale (Fig. 1). This action is renewed each summer, choking airways with fallen slate, tearing down trolley wires, hampering haulage, endangering men and adding considerably to the deadwork cost. Only when mines have been worked for a period of years and have been advanced a long distance from the shaft do the active workings become comparatively free of this trouble, and even then the intake entries are still a source of much deadwork. Such was the annoying situation at the mine of the Saxton Coal Mining Co. operated in the No. IV coal just north of Terre Haute, Ind. During the months of warm weather it was possible to stand at any quiet spot in the mine and within 10 min. hear at least two or three falls,

Jan 1, 1931

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Frederick Laist

THE object of the construction and operation of the 80-ton leaching plant was to test out the leaching of sand tailings on a large scale and, if possible, determine a definite method of operation, and the best construction for the larger unit which is now being built. It was also of importance to obtain some practical data as regards cost items. The 80-ton plant was not expected to be a commercial success. A leaching process on such low-grade material necessitates the treatment of a very large tonnage.. Such a cost item as labor, for instance, is entirely out of proportion in such a small plant. The amounts of acid, salt, scrap iron, and fuel for roasting, however, are the same per ton in an 80-ton plant as in a 2,000-ton plant. These costs were definitely established. Also the percentages of extraction and grade of tailings were definitely determined for a large-sized unit. Following will be found the description of the plant, the method of operation and the results obtained. A -general view of the plant is given in Fig. 1. The bins consisted of one coal bin with a capacity of 30 tons, one salt bin with a capacity of 20 tons, and a "mill tailings" or feed bin which held 70 tons. The coal and salt bins were placed with their floor level even with the firing floor of the roasting furnace. The feed bin, to give it greater capacity, discharged about 12 ft. below this point, to a 12-in. conveyor belt, which, in turn discharged into a pug mill. This fed another conveyor belt, which discharged into the top hearth of the furnace. The furnace was an ordinary six-hearth MacDougall roaster, .20-ft. in diameter. It was equipped with two fire boxes, on opposite sides, the flames entering on the third hearth. An induced draft was obtained with a Buffalo blower, worked as an exhaust fan. Just above the top hearth was an annular flue around the whole circumference of the furnace. Slots at intervals of about 18 in. led from this flue down into the top hearth. The slots were 2 in. wide by 6 in. long. This annular flue proved rather unsatisfactory, as it tended to fill up with flue dust and choke the slots, thus cutting down the draft. The volume of gas through

Jan 8, 1914

By M. S. Smani, P. Blazy, J. M. Cases

Investigations on the beneficiation of sedimentary Moroccan phosphate ores are reported in four separate parts. The first discusses electrochemical phenomena at the solid-aqueous solution interface for minerals of the apatite group. In the second part, the electrochemical properties of the calcareous gangue associated with the phosphate ore are investigated. The flotation of calcite and phosphate oölites, using both anionic and cationic collectors, is discussed in the third part. It is shown that selective recovery could be obtained for precise concentrations of collectors and pH ranges. Results of work aimed at optimizing depression of phosphate oölites during inverse flotation of the carbonate gangue with sodium oleate are reported in Part 4.

Jan 1, 1976

Boundary and general corrosio~z rates for higkpurity alutninum were ~rzeasured irz 16 pct HC1 at sJmllow penetrations (< 25 p). The rates for several high-angle random tilt boundaries, several [001] synzmetrical tilt boundaries, a 54-deg [010] twist, and a 15-deg randorn tw~st boundary were one-fourth to one-third higher than that of the (001) surface used as reference. Boundary attack was slower for 23 and 37-deg [001] tilt boundaries and a 16-deg [010] twist boundary. The corrosion rate for a (111) surface was roughly om-third higher than for (001) and was thus about as high as the corrosion rate of the fastest boundaries. The boundary attack did ?lot appear to parallel the variatiorz of boundavy energy. The signvicance of the anisotropy of corrosion was discussed.

Jan 1, 1966

By G. P. Connell, R. E. Gilmore, J. H. H. Nicolls

The purpose of this paper is to suggest a procedure for indicating the dividing line between noncaking coals and those that have weakly caking properties. A laboratory agglomerating test as an aid in classifying weakly caking coals is outlined and its merits in comparison with the standard agglutinating method advanced by the U. S. Bureau of Mines are discussed. No attempt, however, is made to discuss in detail either the different methods for determining "caking" and "agglutinating" indices or the various systems of classification. Two methods, differing somewhat in procedure, have been employed and recognized as suitable for determining the caking or agglutinating values of coals; namely, those in which an inert material such as sand, electrode carbon, etc., has been mixed with the coal before being heated, and those in which the coal is carbonized alone. In all such methods, the coal with or without the inert material is in the finely divided state and the index or value sought is derived from the examination of the residue after heating in a closed crucible or other container. The procedure outlined by Selvig, Beattie and Clellandl is the most recent representative of the method using sand as inert material, while the agglomerating test described below is representative of the method in which the coal is carbonized alone. The standard volatile-matter determination affords a means for observing the coking properties of a coal, and this has been described by Rose2 as the simplest of all coking tests. According to him, "the resulting coke button will indicate whether the coal is noncoking, feebly coking or strongly coking," despite the fact that "almost every condition in this test is at variance with large-scale carbonizing practice." Lessing,3 the

Jan 1, 1934

By K. C. Strebig, C. W. Schultz, A. A. Selim

The effect of some organic additives in diamond drilling of quartzite was investigated in the laboratory. The drill was designed to measure the rate of penetration, the thrust, and the torque and to record each as a function of the distance drilled. A statistical plan was followed throughout the investigation and an equation representing the bit performance was derived from the mathematical theory of reliability. The drilling torque was found to increase with the use of additives while the sliding coefficient of friction and the wear coefficient decreased. The energy per unit volume consumed was found to increase with the use of additives. A hypothesis explaining the effects achieved with the additives is given. INTRODUCTION For some time researchers have attempted to increase drilling efficiency by adding certain agents to the flushing medium. Much of this interest is the result of the observations of Rehbinder, Shreiner and Zhigach1 They postulated that "...in processes for the mechanical destruction of solids, a region of increased crack formation is created in the deformed layers adjoining that surface of destruction, forming the predestmction zone. The surrounding medium (for example, a liquid) which wets a given solid will penetrate the embryo microcracks of the predestruc-tion zone. Increasing the molecular affinity of this liquid for the surface of the solid considerably facilitates the deformation and destruction by softening the solid in the zone of increased crack formation. In this manner, the hardness or strength of the deformed body is decreased by the influence of the penetration of the liquid into the predestraction zone." This is known as the "Rehbinder effect". Rehbinder&apos;s work has prompted many investigators to examine the effect of additives on the mechanical destruction of rocks. Engelmann, Terichow and Selim reported that the maximum penetration of the rock by a diamond point in a solution environment was at the isoelectric point of the solution.* Robinson reported that his results did not appear to support the theory of Rehbinder.3 Joris and .McLaren suggested that additives with surface tension lower than water will be more efficient in cooling the diamonds.4 Their effectiveness in removing the fine cuttings from the face of the bit will also improve the efficiency of the system. They reported an improvement in impregnated bit life and penetration rates with the use of soluble oil additives. In contrast, Long and Agnew, drilling with surface set bits, reported that lubricating agents increase bit temperature and wear.5 A significant change was reported6 in the mechanical properties of rock with polar additives. It was concluded that this change in the mechanical properties of the rock in the presence of the additive is due to the rock hydrophilic properties. Ethylene glycol, glycerine and anionic detergent were selected for this investigation because their surface tension is lower than that of water. The surface tension of these additives for the concentrations studied was 42 to 75 percent of the surface tension of water. A low surface tension additive would wet the surface of the diamonds more easily and hence would be more effective in cooling the diamonds. Another characteristic of these low surface tension additives is their effectiveness in removing the cuttings and preventing the flocculation of the formed particles in the drilling process. This article summarizes the results of an investigation performed at the laboratories of USBM, Twin Cities Mining Research Center. The objective of the investigation was to study the over-all effects of some organic additives on the performance of diamond impregnated bits in atmospheric drilling conditions only and not in downhole pressured conditions.

Jan 1, 1970

By W. A. Foster

NINETY years after the Riddle nickel deposit N was discovered in Oregon in 1864, Hanna Coal & Ore Corp. began mining operations. Until 1954 much prospecting and preliminary development work had been done on the property, but no ore had been shipped other than for metallurgical testing. The deposit is being explored by churn drilling and trenching, and a few test shafts have been put down for the purpose of studying the ore in place, determining volume and moisture factors, and gathering bulk samples for pilot plant and smelter tests. In churn drilling, 6-in. casing is driven down 2 or 3 ft behind the drill bit and bottomed at each 5-ft interval. All the sludge for each cased 5-ft interval is dumped through a splitter and one eighth is saved and analyzed. Drillholes are stopped after going through the ore zone and penetrating fresh peridotite in which the nickel content is less than 0.5 pct.

Jan 8, 1957

By John S. Johnson, Thomas Fraser

SIZING is the process of separating mixed particles into groups of particles all of the same size, or into groups in which all particles L range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola 1 described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes2 in the mine working places to recover coarse coal. This mining procedure left the fines in the mine. Preparation outside the mine started with the installation of stationary cast-iron plates with 4 to 6-in. square holes. The run-of-mine coal was dumped upon the platforms, the large pieces of rock were picked out by hand, and the large lumps of coal were broken with hammers. The term "breaker," which still applies to the anthracite-preparation plant, originated with this practice, but the term is no longer descriptive of the entire function of the plant. In 1884, the first power-operated anthracite coal breaker3 was erected by Gideon Bart at his colliery at Wolf Creek near Minersville, Pa. This plant utilized a system of rolls for breaking the coal and revolving screens for sizing. The plant was driven by a steam engine. It could handle

Jan 1, 1943

By G. H. Matheson, J. M. W. Mackenzie

The flotation rate of coal has been studied using a continuous laboratory flotation cell and a multiple exposure photographic technique. The effects of particle size, reagent additions and cell turbulence on the flotation rate of coal have been investigated. The results have been analyzed in terms of current theories of particle bubble encounter and adhesion. The rupture forces which occur during particle bubble encounter have been shown to have an important effect on the flotation rate of coarse coal particles. The flotation of coal is a time dependent process, and in order to obtain a complete understanding of the operation it is necessary to determine the kinetics of the process. In coal flotation, the flotation rate and the associated values of cell productivity in terms of tons per kilowatt-hour and tons per cubic foot of cell volume are of greater importance than in most other mineral flotation operations. The reasons for this are associated with the low unit value of coal and the relatively high cost of coal flotation compared with other coal cleaning processes. An important aspect of coal flotation kinetics is the design of coal flotation cells. The cells used in many coal cleaning operations are often replicas of those used for the treatment of sulfide ores and are not necessarily suitable for the treatment of coal washing pulps, which usually contain a higher percentage of coarse and floatable material than the sulfide pulps for which the cells were designed. This disadvantage of many coal flotation cells has been recognized by Russian engineers who, by the addition of baffles to their subaeration coal flotation cells have increased the cell capacity by 100%. Investigation of the variables which influence flotation kinetics and cell productivity are, therefore, important to the coal industry where flotation is the only accepted method of cleaning the fine (-1/2mm) coal. The kinetics of the flotation process have been investigated in detail by Schumann10 who developed a continuous flotation cell which permitted the study of flotation under steady state conditions. This technique has been used by Gaudin et a1.,6 Brown and Smith and recently by Jowett and Savfi.7 The latter authors have developed a refined mathematical treatment for interpreting the results of continuous laboratory tests. Attempts have also been made to study flotation kinetics using conventional batch testing techniques. The experimental difficulties, however, and the problems of determining the order of the flotation rate process have made this technique of dubious value. A summary of the proposed rate equations for batch testing and the difficulties associated with this technique is given by Brown and Smith. 2 The experimental techniques described above are concerned with the rate of production of froth product. However, several authors, notably Sutherland, 11 Bogdanov1 and Philippoff, 9 have analyzed flotation

Jan 1, 1963

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10&apos;a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann&apos; in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5&apos;6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1&apos;-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1&apos; ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By A. F. Melcher

The present paper is a progress report on an investigation of the physical factors of oil and gas and especially of their sands,&apos; such as pore space, size of pores or permeability, retentivity, viscosity of the oil, temperature, pressure, thickness and area of the pay sand, water relations, and capillarity. The purpose is to determine as many of these physical factors as possible, and to ascertain the relations existing, directly or indirectly, between these physical factors and the production of oil and gas. As yet only pore space2 and size of grains of pay sands have been investigated, although an apparatus has been designed to determine the permeability of a sand to oil, water, or gas under definite drops of pressure between the entrance face and exit face of the sample. Messrs. E. W. Shaw, R. Van A. Mills, D. Dale Condit, G. B. Richardson, G. C. Matson, and C. H. Wegemann collected the samples upon which the physical determinations were made. Acknowledgment is made to my colleagues of the United States Geological Survey for many suggestions and criticisms; to Mr. Mills for the production data given of the oil wells from which some of the samples were collected; to Mr. A. W. McCoy of the Empire Gas and Fuel Co., Bartlesville, Okla., for many ideas. Determining Pore Space of Oil and Gas Sands In selecting a method for the determination of pore space, two objects were kept in mind: First, the method must not only be sufficiently

Jan 1, 1921

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200°C, a wide range of conveyors is available. Special constructions of rubber conveyor belts. steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400°F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F.

Jan 5, 1953

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild&apos; and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m&apos;Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m&apos; is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m&apos; is not a true thermodynamic equilibrium constant but varies with carbon content.&apos; 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson&apos;s paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence&apos; but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

H. H. Bleakney (Dept. of Mines and Technical Surveys, Ottawa, Canada)— The work of Dr. Machlin and his colleagues at Columbia University is so scholarly that one hesitates to take issue with them. Nevertheless the writer feels compelled to enter a demurrer to the mechanism of intercrystalline cracking proposed in this paper. The principal obstacle to its acceptance is found in its preoccupation with purely mechanical influences and its disregard for the chemical effect of impurities. The writer believes that the destruction of metallic cohesion by concentration of impurities at the grain boundaries is a necessary and sufficient condition for the development of intercrystalline cracking; and he believes that discussion of the numerous mechanical explanations proposed should wait until some valid objection to the chemical hypothesis has been advanced. It is nearly twenty years since Gillett" drew attention to the possibility that the chemical influence of precipitation might be the cause of intercrystalline cracking. As early as 1935, Greenwood&apos;" remarked that grain-boundary precipitation of impurities in lead appeared to promote intercrystalline cracking. Again in 1939, Scott commented as follows on a paper by Thielemann and Parker:&apos;" "There are at least two familiar phenomena that can influence grain-boundary cohesion: 1) intergranular oxidation; and 2) grain boundary precipitation. An important consideration in this work, therefore, is to determine which, if either, of these factors is responsible for the low values of cohesive strength observed." In 1952. the writer presented evidence," some original and some abstracted, which indicated that in copper, silver, aluminum, lead and iron, intergranular cohesion was a function of the purity of the metal. In 1954 Glen, discussing a paper by Ridley and Tapsell14 indicated his belief in a precipitation mechanism for the intercrystalline embrit-tlement of molybdenum steel and suggested that with an absolutely pure metal it would be almost impossible to obtain an intercrystalline crack. This suggestion has

Jan 1, 1959