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By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.' Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan' has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock' found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By R. Grierson, R. N. Parkins

The m.echanica1 properties, at high lzomologous temperatures, of the intermetallic compounds InzBi and Mg17A112 were measured as a .function of temperature, applied strain rate, previous thermal and mechanical history, and composition. Mgl,Al12 was investigated ilz compression, whereas Zn,Bi was investigated in tension. A decrease inflow stress with increasing strain was observed jor both alloys. The results obtained are discussed in terms of the dislocation-multiplication processes in these materials. MANY intermetallic compounds are reported to undergo a brittle-ductile transition at high homologous temperatures.' There is evidence in the literature that some of these compounds exhibit a large yield drop when plastically deformed.'j3 Both of these forms of behavior are shown by the covalent elements germanium and silicon4,5 and also by certain ionic compounds.8 The present work is a study of the deformation, at high homologous temperatures (>2/3 Tm), of two intermetallic compounds, In2Bi and Mg17Al12. InzBi has a disordered hexagonal structure7 (c/a = 0.598) and a solubility range of 32.3 — 33.2 at. pct Bi.8 It has a melting range from 72° to 89°C. Mg17Al12 has an ordered bcc (A12 type)7 structure and exists over the range 50 to 60 at. pct Mg8 with a melting range from 437° to 462°C. We have been unable to find any reference to previous investigations of the mechanical properties of BiIn,. Novikovg has reported that cast samples of Mg17A112 show ductility, when bend-tested, at temperatures above 380°C. EXPERIMENTAL Ingots of In2Bi and Mg17Al12 were melted under an argon atmosphere and cast, in situ, in a graphite crucible. The materials used were of 99.99 pct purity. The alloys prepared contained 66.9 at. pct In in the case of In2Bi and 58.4 at. pct Mg in the case of m17A112. The ingots were homogenized and then extruded. Two-in.-diam Mg17Al12 ingots were extruded at 375°C to give 3/8-in.-diam rod. The rate of formation of this rod was 0.25 in. per min. One-in.-diam InzBi ingots were extruded at 20°C, using a rate of 1 in. per min, to give 1/8-in.-diam rod. In both cases the extruded rod had a recrystal- lized, fine-grain, structure. (For Mg17Al12, d = 11.2 µ; for BiIn2, d = 22 µ.) Mechanical-property determinations were made in a hard-beam machine, in tension in the case of In2Bi and in compression with Mgl7Al12. The tensile tests were on specimens having a gage length of 1.1/2 in. and a diameter of 1/8 in. The compression tests on Ml7A112 were on specimens of 3/8 in. diam by 3/8 in. high and the ends were coated with poly-tetrafluorethylene to minimize friction. RESULTS In2Bi. Fig. 1 shows, particularly at the higher applied strain rates, that In2Bi exhibits a marked yield drop as the deformation increases to about 2 pct, after which the material shows neither hardening nor softening up to 15 pct strain. The magnitude of the yield drop, the stress in the region of flow under constant stress (the stress plateau), and the 0.5 pct proof stress were all dependent upon the applied strain rate according to an expression of the form

Jan 1, 1965

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York L. W. FRANCIS, Chairman. WILLARD S. MORSE, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN; Treasurer. LOUIS D. HUNTOON. WILLIAM A. POMEROY Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. ROBERT H. RICHARDS, ALBERT SAUVEUR. Columbia FRANK A. ROSS, Chairman. RUSH J. WHITE, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. FREDERIC KEFFER, FRANCIS A. THOMSON.

Jan 1, 1915

By John M. Hartman

The high temperature of the blast of modern furnaces renders it desirable that the pipe conveying the blast into the furnace crucible shall transmit and radiate as little heat as possible. To accomplish this, the pipe shown in the accompanying sketch was devised and patented. It consists of a slide-valve, leg-pipe, and belly-pipe, which are held together and to the tuyere by a system of levers and links. The slide-valve is superior to the old throttle-valve. The legpipe is formed of two thicknesses of wrought-iron pipe, with a space of half an inch filled in with clay and brick. The belly-pipe is made in the same way as the leg-pipe, and terminates in a globe face to suit the tuyere. The quarter turn is made extra thick, of cast iron, and the cap on the end is lined with clay also. The catches, A, B, C, are merely for convenience in putting the pipe together. The joints D and E are globe faces, and allow the pipe to adjust itself to any angle. The eye-piece is made of violet glass, which cuts off the glare from the bright coals in the furnace and allows a close examination of the interior, so that any water dropping or vapor can be detected. The glass does not become coated with dirt, like mica. Since good running of furnaces is shown by a bright tuyere, it is necessary to have a good eye-piece to examine them. To detach the pipe, a man lifts the weights, the side rods are then slipped off the bell crank under the quarter turn, the link under the belly-pipe is unhooked, and the pipe carried away. The same process is reversed to put the pipe together. The nozzle is changed by taking off the cap, G, drawing the nozzle through the belly-pipe, and inserting another. In this way the change can be made quickly, without taking down the pipe. On the old tuyere pipe bolts with brass nuts were used, which burned up and gave trouble. In other cases key-bolts were used, making it difficult to adjust the pipe. Bolts make too rigid a joint, and there is no provision for movement from contraction or expansion. As the temperature of the blast increases there is more expansion, and where rigid joints are

Jan 1, 1879

By John M. Hartman

THE high temperature of the blast of modern furnaces renders it desirable that the pipe conveying the blast into the furnace crucible shall transmit and radiate as little heat as possible. To accomplish this, the pipe shown in the accompanying sketch was devised and patented. It consists of a slide-valve, leg-pipe, and belly-pipe, which are held together and to the tuyere by a system of levers and links. The slide-valve is superior to the old throttle-valve. The leg-pipe is formed of two thicknesses of wrought-iron pipe, with a space of half an inch filled in with clay and brick. The belly-pipe is made in the same way as the leg-pipe, and terminates in a globe face to suit the tuyere. The quarter turn is made extra thick, of cast iron, and the cap on the end is lined with clay also. The catches, A, B, C, are merely for convenience in putting the pipe together. The joints D and E are globe faces, and allow the pipe to adjust itself to any angle. The eye-piece is made of violet glass, which cuts off the glare from the bright coals in the furnace and allows a close examination of the interior, so that any water dropping or vapor can be detected. The glass does not become coated with dirt, like mica. Since good running of furnaces is shown by a bright tuyere, it is necessary to have a good eve-piece to examine then. To detach the pipe, a man lifts the weights, the side rods are then slipped off the bell crank under the quarter turn, the link under the belly-pipe is unhooked, and the pipe carried away. The same process is reversed to put the pipe together. The nozzle is changed by taking off the cap, G, drawing the nozzle through the belly-pipe, and inserting another. In this way the change can be made quickly, without taking down the pipe. On the old tuyere pipe bolts with brass nuts were used, which burned up and gave trouble. In other cases key-bolts were used, making it difficult to adjust the pipe. Bolts make too rigid a joint, and there is no provision for movement from contraction or expansion. As the temperature of the blast increases there is more expansion, and where rigid joints are

Jan 1, 1879

By Friedrich Wellmer

INTRODUCTION The Ramsbeck Pb/Zn Mine is located in the northern Sauerland area of West Germany, 150 km N of Frankfurt and 120 km E of Cologne. This is a vein deposit which has been worked from the middle of the 19th century to 1974. About 15 million tons of ore were mined and milled. The ore district contains several vein deposits and is roughly 14 km in length and 4 to 5 km in width. The host rocks are strata of Lower Middle Devonian age. The strata strike 60° to 70° NE and where overturned have a dip steeper than the veins (Fig. 1). The galena-sphalerite mineralization is in quartz veins, which are mineralized where they cut the "Main Ramsbeck Quartzite" horizon, a very competent host rock. Vein structures strike at 65º to 75º, dip about 20° to 25º SE and cut the quartzite at approximately 60 m intervals. The main or "steep veins" within each vein structure dip at 10º to 80° SE with an average of 30° and are offset by thrust faults dipping 5º N to 40° S with an average of 5º S. "Flat veins" usually weakly mineralized occur in the thrust faults between the "steep veins", thus forming the overall step-like vein structure. The mineralization is very irregular and changes a- long strike and down dip. It consists of thin veins of pure sphalerite and galena with quartz and pyrite. The thicknesses of the pure sphalerite and galena veins

Jan 1, 1977

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By A. E. Martin, Gerhard Derge

IF the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of diffusion, and electrical conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented as Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags of the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. REVIEW of LITERATURE In 1906 Aiken1 obtained a patent for a continuous process of producing iron electrolytically by passing a direct current through a bath of FeO-SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By C. W. Beattie, R. L. Solter

ALUMINUM-KILLED, low carbon steel sheets are used extensively for severe deep drawing and other difficult forming operations. They usually, but not always, have a characteristic grain structure in which the grains are elongated both in the lengthwise and in the transverse direction. As described by Burns and McCabe,&apos; a typical grain in the plane of the sheet has its two axes in that plane from 1 Y2 to 4 times as long as the axis normal to the plane of the sheet. Rickett, Kalin, and MacKenzieZ have also reported on the recrystallization behavior of such steel. The contrast in grain structures of fully processed sheets of aluminum-killed and rimmed steel is illustrated by Figs. 1 and 2. The elongated grain structure of the aluminum-killed sheet is not developed on all heats or lots of this metal, and studies of the factors controlling and influencing its formation are reported in this paper. Jeffries and Archerb tate that unstrained grains are normally equiaxed, but exceptions are common. For example, if a metal containing a material mechanically obstructing grain growth is subjected to considerable working followed by thorough annealing, it may exhibit grains consistently elongated in the direction of working. Our experiments demonstrate that aluminum-killed, low carbon steel is such a metal, and that the substance mechanically obstructing grain growth is aluminum nitride. The effectiveness of aluminum nitride in inhibiting grain growth has been found to be influenced by the degree of cold reduction, the rate of heating in annealing, the thermal history of the sample before cold reduction, and the residual aluminum content. A correlation between grain shape and austenitic grain coarsening temperature also was indicated and additional experiments demonstrated that aluminum nitride is also the principal cause for the fine grain characteristic of aluminum-killed steels. Manufacture In conventional practice, aluminum-killed sheet steel is manufactured from a low carbon steel containing approximately 0.02 to 0.07 pct residual (HC1 soluble) Al. With the exception of certain samples containing greater or lesser amounts of aluminum, the steels used in these investigations were within the following composition range: C, 0.03 to 0.06 pct; Mn, 0.28 to 0.38; S, 0.017 to 0.032; Al, 0.03 to 0.06; P, <0.01; and Si, <0.01. Properly heated ingots are rolled to slabs about 4 in. thick. After surface conditioning, the slabs are reheated to about 2300°F and hot rolled continuouslv to strip about 1/10 in. thick. The strip rolling is completed at a temperature of 1550°F or higher, and the strip is coiled, usually at a temperature near the lower critical transformation. After cooling, the strip is pickled to remove oxide, cold reduced 40 to 70 pet to final thickness, then annealed to 1250° to 1350°F in 20 to 80 ton charges, the size of which results in slow heating and cooling rates. Effect of Cold Reduction According to Sachs and Van Horn,&apos; the deformations of the individual grains in rolling are similar to those of the total volume. Thus individual grains would elongate in rolling according to the amount of cold reduction imposed. This is true theoretically, but as cold reduction increases the individual grains tend to fragment, and measured grain elongations become less than theoretical. The amount of grain elongation may be described by a numerical rating based on grain counts made by the intercept method. Specimens are polished normal to the plane of the sheet, with the polished surface extending parallel to the rolling direction. After etching, grain intercepts are counted along a 50 mm line on a micrograph of suitable magnification. In random locations parallel to the plane of the sample 20 counts are made and 20 are made in the thickness direction of the sample the average count in the thickness direction divided by the average count parallel to the plane of the sample gives a numerical rating of the grain shape called grain elongation. For example, a grain elongation of 2.00 means that the average grain is twice as long as it is thick. The average of both counts may be converted to grains per sq mm by a nomograph relating intercept counts and grain count. By the same procedure the grain elongation in the plane of the sheet but transverse to the rolling direction may be determined, using transverse metallographic samples. A comparison of theoretical and measured grain elongation was obtained on an aluminum-killed

Jan 1, 1952

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By AIME AIME

CHARLES ALLEN GIBBONS has been in the anthracite industry now since 1931, following his earlier experience in the bituminous fields, which dated from boyhood. In fact he was born in a coal-mining district-at Morgantown, W. Va.-starting at an early age working in the neighboring mines-going to the secondary schools there and then to West Virginia University. After graduating in 1923 with a B.S. in mining engineering he was made assistant superintendent of bituminous mines in southern West Virginia. Less than a

Jan 1, 1939

FROM the first to the last meeting of t h e Rocky Mountain Club John Hays Hammond served as president. He guided its deliberations when there were any, but that always y o u n g organization was never particularly deliberate. Youth never is. And the Club was the embodiment of the youthful spirit of the West, which considers any- thing can be done if there be but the will to do it. Ham- mond and the others came out of the West, but they, brought the West with them P and in all the far countries in which he has served his profession and in all the honorable offices in which he has served his country, he lived true to the ideals under which he was raised. A Californian, born in San Francisco in 1855, the son of an army officer, Major Richard Pindell Hammond, educated in the public schools of his native city, at Yale, and at Freiburg, he turned early and quickly to mining. He served his apprenticeship as all successful mining men do, as assayer, surveyor, as assistant in ex-aminations and later as principal, and finally as mine manager. Even in those days of beginnings, his future world-wide career was foreshadowed in that Mexico as well as California served as his training school. His first major step up the ladder was in connection with the Bunker Hill and Sullivan mine, where he served in various positions finishing as president and considerable owner. It was from this great lead mine that he was called to South Africa, where he remained a number of years and was the technical expert who guided the great enterprises of Barnato Brothers and Cecil Rhodes. The story of his activity in developing the "deeps" of the Rand and in opening Rhodesia has been often told but is always an alluring one of adventure and accomplish-ment. After his famous escape from death at Johannes-burg as a member of the Reform Committee, he went first to London and later returned to the United States representing both British and American capital in the purchase and development of great mines in all parts of the world. For some years he was general man-ager, consulting engineer, and director of the Guggen-heim Exploration Co., but of recent years he has oper-ated entirely on his own account and with marked success.

Jan 4, 1928

By P. S. Rudman

Laves phases, AB2, are considered as Izerrzisub-stitutional solutions m1hich are defined by a one-for-truo replacement scheme. Atomic-size tnisfit is considered in terms of deviations of the ratio 2V°b/V°A from unity, where v° = atomic volume. A simple elastic model has been used to calculated deviations from "Vegard&apos;s law of atomic vol-umes". Comparison has been made between calculated and observed atomic-volume deviations fov 222 Laves phases. Agreement is generally very good although there ave some few exceptions which appear to be excusable in terms of electronic changes that ore beyond the scope of the present model. We can consider the formation of a binary sub-stitutional solution A-B from an A solvent as one-for-one replacements of A atoms by B atoms. As the atomic-size ratio deviates from unity, the solution becomes thermodynamically less stable and hence more restricted because of atomic-misfit strain energy. In accordance with our previously presented conclusion1 that the atomic volume, v, is in general the most appropriate measure of atomic size, the ideal size ratio for a binary sub-stitutional solution is vg/vA = 1. The Laves phases have been described by Berry and Raynor2 in terms of various stacking sequences of hexagonal layers of B atoms for the three structures MgZn2(C14), MgCu2(C15), and MgNi2(C36). To form the Laves phase of ideal composition AB, we start with complete hexagonal layers of B atoms in the appropriate stacking sequence and we remove, according to an appropriate scheme for each structure, two out of every four B atoms and replace the two removed atoms by one A atom. We thus might expect to find that the ideal size ratio for the Laves phases is 2v/B/ VA= 1. From this point of view, then, we call Laves phases hemi-substitutional solutions since we employ one-for-two replacements. By analogy with substitutional solutions we can expect for Laves phases that as the ratio 2VB/Va deviates from unity the phase occurrence will be more restricted. Laves3 has plotted the distribution of Laves phases as a function of the radius ratio, ?A/rB, and found that, while the distribution extended from 1.05 < rA/B < 1.50, the

Jan 1, 1965

By A.E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By A. E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By J. J. Frawley, W. J. Childs

PREVIOUS studies have shown that if a supercooled liquid metal was perturbed by vibration the probability of nucleation is is During a recent investi- gation to determine quantitatively the amount of energy needed to cause nucleation in a given supercooled liquid specimen, it was found that at low-energy values in the megacycle range, below the threshold energy value for cavitation, the amount of dynamic supercooling was greater than the amount of static supercooling. That is, if a specimen had a given amount of thermal supercooling under static conditions, its thermal supercooling could be increased by the addition of low-energy sound waves. The material used in this investigation was high-purity bismuth. This material was chosen because of its low melting point and the high degree of supercooling which could be easily obtained. The sound gener- ator employed in this work was a commercially built Sperry ultrasonic testing unit. This unit was equipped with a barium titanate crystal as a piezoelectric transducer. These sound waves were transmitted to the supercooled melt by a Pyrex rod, as shown in Fig. 1. The transducer was coupled to this Pyrex rod wave carrier by motor oil. The Pyrex wave carrier was approximately 1.5 ft long to prevent damage to the transducer by heat. The diameter of the Pyrex wave carrier appears to be critical. In the initial tests a wave carrier of 0.5 in. in diam was employed. However, the sound waves had no effect on the amount of dynamic supercooling. When the diameter of the wave carrier was increased to approximately the inside diameter of the Pyrex crucible, the sound waves were more effective. Approximately 200 g of metal was melted under a stannous chloride flux in a 30-ml beaker by induction heating. The temperature was recorded by a Pyrex-encapsulated chromel-alumel thermocoule which was placed in the beaker after the bismuth melted. The Pyrex wave carrier was immersed slightly below the surface of the liquid bismuth and the specimen was reheated to about 500°C. It was observed that the amount of supercooling depends on the amount of superheating the specimen receives; therefore, for meaningful results the amount of superheating was the same for all heating cycles. The specimen was allowed to cool in air and the change in temperature was continuously monitored with a potentiometric strip-chart recorder.

Jan 1, 1969

G. SHERBURNE ROGERS,* Washington, D. C. (written discussion?).- We are indebted to Captain Lucas for an interesting contribution to the literature of the salt-dome oil fields, and especially for his suggestion that a more aggressive method -of prospecting be adopted. The occasional discovery of new fields on, the Gulf Coast is in itself sufficient to show that the oil possibilities of the region are by no means exhausted, and those who have studied the area most thoroughly are the most optimistic regarding its future. Nevertheless, the search for new fields, according to present methods, involves the expenditure of great sums of money annually, for the proportion of dry holes to producing wells drilled yearly in the Gulf Coast region is much&apos; greater than in most areas, even if all the wells drilled in what is commonly regarded as proved territory are included. Not only are the present methods of locating new domes very uncertain, but when a dome is discovered there is no assurance that it will be oil-bearing; or, if so, whether the oil occurs in the cap-rock, in the sands above it, or in some small isolated lens of sand far down on the flanks of the salt mass. As Captain Lucas points out, about all we positively know is that the domes are there and that some of them are oil-bearing; their origin is a matter of controversy and the original source of the oil is conjectural. Under these conditions, it is not surprising that the search for oil is conducted more or less blindly and that dry holes are common. Many wells are drilled each year in an endeavor to find oil at depths of 2000 or 3000 ft. (609 to 914 m.) or less, in locations which most geologists would condemn without hesitation. As Captain Lucas suggests, the money spent in this way might be used to far better advantage in, drilling one deep well in a carefully selected locality. Opinions may differ as to whether such a, well would find oil, and many geologists will probably believe that the chances are against it, yet all will agree that the boring, whether it finds oil or not, will probably throw light on the origin of the domes and on the source and mode of accumulation of the oil, and will therefore be of great interest, not only to the scientist, but to the oil operator.

Jan 10, 1918

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.&apos; In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.&apos; The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.&apos; Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969