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By E. H. Griswold

The surveying of oil wells has in recent months become a common practice in the deep fields of the Mid-Continent area. Borehole surveys have been made by mining companies for many years, but the introduction of such methods into the oil fields has been delayed until the past few years, because the value of survey data was not fully appreciated. The acid and gelatin bottle methods of obtaining the angle of deviation and the floating compass method of obtaining the direction of horizontal drift have been in use for more than 20 years. A photographic recording instrument consisting of a plumb bob, magnetic needle and electrically operated camera was devised and used in the Rand mining fields of South Africa prior to 1912.1 Another and improved photographic instrument, depending upon orientation of the drill pipe instead of polar magnetism for direction, has been invented and used. The acid bottle method has also been used in conjunction with oriented drill pipe. The magnetic compass is not reliable for oil-well work because of the unsymmetrical attraction of the needle to the well casing and possible magnetic formations. Many engineers also concur in the opinion that orientation of the drill pipe from instrument to surface will be inaccurate because of the torque exerted between the drill pipe and walls of the hole, causing the lower sections of pipe to twist. When it is considered that 4000 ft. of 6 in. drill pipe has approximately the same slender-ness ratio as 6 ft. of silk thread, such twisting effects can be readily visualized. The gyroscopic compass has been suggested for use in direction finding, but the high cost of such instruments will prohibit their use, except in special cases. Due to the lack of accurate direction-finding instruments, almost all of the survey work in the Mid-Continent fields has been of the acid bottle method alone.

Jan 1, 1929

By R. Shuttleworth, R. Smith

A Knudsen effusion tnethod I~as been used lo measure the vapor pressure of pure iron in the temperature range 1000° to 1500°C. Neutron-irradiated , natural iron was used and the Mn'~proclzdced by the (n, p) reaction removed by evaporation at high temperature. The results can be represented by the equation: where pM - 1.088 x 107 atm and T, = 20,890°K. A value of 100.2 kcal per g- atom was obtained for AH;. THE vapor pressure of pure iron in the temperature range 1000" to 1500°C has been measured. Radioactive iron and a Knudsen cell technique were used and the Mn' produced by an (n, p) reaction removed by evaporation at high temperature. From the variation of vapor pressure with temperature values of the enthalpy and entropy of solid iron have been found. Previous workers2 used a Lang-muir method and measurements were made over a smaller temperature range than that in this work. EXPERIMENTAL The apparatus used was similar to that of Pyle and Shuttleworth, and McLellan and Shuttle worth. However, because of the higher temperatures the Knudsen cell was machined from tungsten bar and the flanged furnace tube was beryllia. Heating was by passing a high current (70 amp at 7 v for 1500°K) through a strip of tantalum foil laid across the top of the cell and through a turn of molybdenum wire around the furnace tube. This method of heating ensured that the top of the cell was slightly hotter than the base and prevented condensation and re-evaporation from the orifice. The temperature was measured by means of a pt/Pt 13 pct Rh thermocouple spot-welded to the base of the crucible. To ensure accurate temperature measurement the iron was in the form of a thin disc (0.75 cm diam by 0.075 cm) which lay on the base of the cell. The high-purity iron was irradiated in the Harwell pile for a week at a neutron flux of 1.2 X 10" neutrons per sq cm per sec. The isotopes fe'~ and Fe" are produced by (n! y) reactions but only Fe", half-life 45.1 days, is a emitter; Mn which is also a y emitter, half-life 300 days, is produced simultaneously by an (n,p) reaction.' Immediately after irradiation of natural iron the ratio of ~e" to Mn y activity was 100:l. However, manganese is very much more volatile than iron and almost all the y activity of the condensate is due to Mn'~. Thus it was essential to eliminate all the manganeses before any measurement of the vapor pressure of iron was made and this was done by preliminary heating for 20 hr at 1400°C. For each determination the iron was dissolved from the target with acid and the y activity compared to a known weight of iron. By means of a y-ray spectrometer the y-activity measurements were made at the 1.09-mev peak of the 17e5' spectrum where the background was of the order of 3 cpm. Despite the low specific activity of ~e" a mass of 10- " g of iron could be determined corresponding to a vapor pressure of about l0-'' atm. RESULTS The vapor pressures were calculated from the equation: Where m is the mass of iron effusing in a time t through an orifice of area a2, r is the radius of the target, Z is the distance from the orifice to the

Jan 1, 1965

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach deposits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits. The principal titanium mineral used is ilmenite, but as soon as that mineral began to be sought as a titanium ore, it was obvious that there are ilmenites and ilmenites. Textbook ilmenite should have the composition FeOTiO2 and should analyze 52.6 pct TiO2 and 36.8 pct iron as Fe. The Indian ilmenite, for almost a generation the standard ore for manufacturing pigment in the U. S., was found to analyze about 60 pct TiO, and only 24 pct. Fe, and most of the iron is in the ferric condition. The whole process of pigment manufacture in the U. S. was built up on the use of a raw material of that grade, and the American chemical engineers who operate the pigment plants shuddered at the thought of using a rock ilmenite with 45 pct or so of TiO, and nearly 40 pct Fe. Intensive search was made around the world to find other deposits of rich black sand, like the Indian beaches, but although a few were found, there was some objectionable feature about each. A deposit in Senegal, south of Dakar (Fig. 7), was worked for a while, but an organic coating on the grains made attack by acid difficult. Modern practice would have included a scrubbing operation, in a caustic soda bath, to eliminate the organic coating. Brazilian deposits were numerous, but individually small, and shipping from them difficult. Deposits on the east coast of Ceylon had many attractive features, but the ilmenite analyzed only 54 pct TiO2 and could have been used only with a penalty. Sand deposits with 2 pct ilmenite, like those now worked in Florida, would not have been considered commercial ore, even if they had been known at that time. Most rock ilmenites are associated or mixed with hematite or magnetite, which accounts for the lower titanium and higher iron values than in the sand ilmenites. The Norwegians, English, and Germans, with cheap Norwegian rock ore at hand, learned to install in their pigment plants adequate capacity on the black side, as it is calltd, and counterbalanced the extra cost of plant, and larger amount of acid used, by the lower cost of ore. When World War II arrived, two of the largest pigment manufacturers in the U. S. had to learn how to use the Adirondack ilmenite, but one of them very gladly went back to sand ores when the Florida deposits came into large-scale production after the war. The other continues to use Adirondack ilmenite and finds it commercially attractive to do so. Rutile is not a raw material for titanium pigment manufacture by the sulfate process, since it is insoluble in sulfuric acid. In addition to its small consumption in chemicals and ceramics it began to be used in quantity in welding rod coatings. With the outbreak of World War 11, and the tremendous need for welding rods in shipbuilding and other structural steel construction, rutile suddenly became in heavy demand. The sand deposits on the eastern shore of Australia (Fig. 8A) which had been worked in a small way since 1934 were brought into production, and some stream placers in Brazil were worked and rutile concentrates shipped to American

Jan 1, 1960

By Y. Astafyev

In applying computers at the enterprises it is necessary to develop an open-pit model which completely corresponds in its structure, properties and characteristics to real open-pit mining. This model is used for controlling open-pit operations which ultimately define the system controlling ore reserves. The preparation and reserving of the latter are highly expensive and labour-consuming, therefore the investigations are aimed at developing the ore reserve control system which is capable to provide open- pits with the necessary ore reserves on the basis of equipment relibility characteristics, and thus helps to solve the ore reserves problem which is to define their optimum dimensions under conditions of stochasticity of production processes. In accordance with the tasks of the investigation it may be conventionally divided into three parts. The aim of the first part is to develop a structural open-pit system model consisting of a set of elements which are represented here by drill-rigs, shovels, trucks, unit trains, plant receiving bins and dumps (Fig. 1). The combination of similar elements makes up technological components the sequence of which forms simple systems. The latter, in their turn, grouping according to the type of mined rocks and inter- acting in parallel, form the "Stripping" and “Mining” subsystems. In addition to this, there is the "Ore Reserves" subsystem which serves as a "store" and includes opened-up, prepared and ready for extraction ore reserves.

Jan 1, 1977

By T. O. Massalski, J. D. Ayers

A massive transformation, 0 —am, takes place in a number of copper-based systems where the ß phase field at high temperatures extends to compositions that are slightly less solute-rich than the limits of the a phase field that exists at lower temperatures. Consequently a solid-state transformation becomes possible that does not involve a change of composition. Within this narrow range of composition the massive am phase can be usually produced in two ways: by a fast quench from the ß phase through the a phase field, or by pulse heating into the a phase field of an undecomposed ß phase retained at room temperature by a prior quench. In the Cu-Ga system the occurrence of a massive am phase has been also observed in alloys whose composition falls outside the equilibrium a phase field1 but not in the Cu-Zn system.2 We have recently observed the occurrence of the ß — am transformation also in two silver-based systems, Ag-Zn and Ag-Cd. The a and 0 phase fields in these systems again slightly "overlap" in a narrow composition range. In the Ag-Zn system this range falls between 36.7 and 40.2 at. pct Zn, and in the Ag-Cd system between approximately 41 and 42.5 at. pct Cd. Alloys were prepared from high-purity materials and cast in quartz tubes under inert atmosphere. No significant change of composition occurred during casting. After homogenizing in the 0 phase field, small pieces of each alloy were reheated at the homogenizing temperatures for a few minutes and quenched into various media. There were examined metallographic-ally after removal of surface layers that may have suffered from contamination or from the loss of the solute element. In the Ag-Zn system extensive areas of the am phase (identified by selective etching, observation of the slip trace variants, and occurrence of twinning) were observed in a comparatively low-zinc alloy (37.8 at. pct Zn) for all quenching media employed: iced

Jan 1, 1969

By R. H. Pemberton

The principle of airborne electroniagnetic prospecting is well-known. 'The basic geonhysicai texts in inost cases discuss the main elements involved in electromagnetic prospecting. However. there is ceriainlv iittle information available to the public concerning he present types of airborne eiectromagnerlc systenis being flown today by both contracting companies and some of the mining companies which have their own instruments. This is unfortunate since it is difficuit for those people not conducting such operations to understand thoroughly the iarge variation in the electromagnetic instrunlents available. Basically, the aeriai electromagnetic induction method utilizes a primary or transmitting coil through which is generated an alternating magnetic field at a frequents: generally of the range of 100 to 2000 cycies per sec. This primary field links with buried conductors and generates eddy currents within them. These eddy currents in themselves generate a secondary magnetic field of the same frequencv, but generally nut-of-phase with respect to the prinlarv field. This secondarv field is detected above the ground in the pick-up or receiver coil which is tuned to the frequency of the current applied to the primary transmitter coil. One of the main problems in the development of an airborne electromagnetic system is that of maintaining constant coupling between the cransmitting and receiving coil systems. Any variations in the coupling due to relative motion between the two coils will result in an in-phase signal being induced in the receiver coil. [However, any variation in the coupling does not result in an out-of-phase signal change in the receiver coil. The first airborne eiectromagnetic svsteins which were developed utilized a large prlniarv coil set up on the aircraft with the receiving coil being towed behind in a bird, generally at the end of a cable of about 500 ft. in length. It is possible with such a system to record the out-of-phase or quadrature responses more readily than the in-phase re-sponse. One system utilizes a dual frequency method, wnereby the out-of-phase responses at two frequencies are recorded. Another system used today records a single-frequency olrt-of-phase response. Recentlv home companies have succeeded in measuring from ne air both the out-of-phase and the in-phase components. The usefulness of recording in-phase is weil-known, but unfortunately this is difficult to obtain in any towed-bird system. In order to measure the true in-phase signal, the most straightforward system is that in which both the transmitter and receiver coils .Ire affixed in space so that there is little or no relarive motion between the two coils. THE FLIGHT SYSTEM The particular system which Canadian Aero Service is using at present is mounted on a Sikorsky S-55 helicopter (Fig. 1). A record of both the in-phase and out-of-phase responses is made at a frequency of 390 cycles per sec. The transmitter coil is set on a boom mounted in the front of the helicopter; the receiver is set on a tail boom extending back from the helicopter. Separation between these coils is about 65 ft. The two coils are mounted in a vertical co-axial relationship. Having the transmitting coil in a vertical plane ensures that maximurn coupling will occur with vertical conductors rather than flat-lying conductors. Having them mounted as they are in a co-axial relationship on the helicopter ensures that maximum response will occur when the flight direction is orthogonal to the strike direction of a given conductor. The present sensitivity of the Em system is 20

Jan 1, 1961

By Laurence Delisle, Aaron Finger

THE alloys formed by the addition of nickel to iron by convelltional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.? owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect could be obtained in alloys of iron and nickel prepared by powder metallurgy technique. PROCEDURE Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, 0.001 5 ; lead, 0.035; tin, 0.025 ; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A representative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 3 2 5-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the surfaces of the particles. The reduced powders, slightly caked, were ground in a mortar and screened again through a 325- mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hydraulic presses. The pellets were compacted in a cylindrical die, ½ in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specifed for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By Calvin Pierson, R. S. Dean, E. P. Barrett

Wrought iron and steel have been prepared from limonite, hematite, and magnetite ores by gaseous reduction, compacting and squeezing the resulting product at high temperature and finally melting the wrought iron so formed. The structure, analyses, mechanical and magnetic properties of the products are given. It is found that the structure of iron ores is best studied by subjecting them to gaseous reduction and using metallographic technique on the resulting sponge iron. In this way the cell structure of iron ore is clearly shown. The wrought iron made by heating compacted sponge iron to 1450" C., and forging, shows a cell structure inherited from the ore. This cell structure is further preserved in melting and casting the wrought iron. The probable relation of the properties of the materials to this inherited cell structure is discussed.

Jan 1, 1935

By Calvin Pierson, R. S. Dean, E. P. Barrett

Wrought iron and steel have been prepared from limonite, hematite, and magnetite ores by gaseous reduction, compacting and squeezing the resulting product at high temperature and finally melting the wrought iron so formed. The structure, analyses, mechanical and magnetic properties of the products are given. It is found that the structure of iron ores is best studied by subjecting them to gaseous reduction and using metallographic technique on the resulting sponge iron. In this way the cell structure of iron ore is clearly shown. The wrought iron made by heating compacted sponge iron to 1450" C., and forging, shows a cell structure inherited from the ore. This cell structure is further preserved in melting and casting the wrought iron. The probable relation of the properties of the materials to this inherited cell structure is discussed.

Jan 1, 1935

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By Terkel Rosenqvist

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp p/RT, where p is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By J. F. Butler, H. W. Paxton

The vapor pressures of manganese in equilibrium with several alloys in the iron-manganese-carbon system between 1200° and 1275°K have been measured using the Knudsen effusion technique in conjunction with a vacuum microbalance. The effect of orifice area of the effusion cell upon the measured pressure has been determined. The binary iron-manganese system shows small negative departures from ideality, and the system of mixed carbides, (Fe, Mn)7C3, in equilibrium with graphite behaves ideally. THIS work is a continuation of the investigations in which the Knudsen effusion method has been used to determine thermodynamic activities in systems and at temperatures of interest to metallurgists. In a previous publication,' the free energy of formation of Mn7C3 was determined and some preliminary work on the solution behavior of this carbide with the hypothetical "Fe7C3" was reported. The present work deals with this latter topic and also includes data on the binary ir-on-manganese system. EXPERIMENTAL METHOD The Knudsen effusion method was used to measure the vapor pressure of manganese in both the alloy and carbide sections of this investigation. This dynamic method of vapor pressure measurement presents a problem when studying solid alloy systems in which one of the components has a much larger vapor pressure than the others. Over-all depletion of the alloy in the most volatile component will occur during evaporation so that the pressure of that component will decrease. Even more serious than the over-all concentration change is the surface depletion of volatile component in the alloy brought about by the slow rate of diffusion of this component from the interior to the surface of the solid particle. Since knowledge of this surface composition is necessary in order to relate it to the activity determined through the measurements, changes in surface composition from the analyzed bulk composition are to be avoided in dynamic vapor pressure studies of solid alloys. The system under investigation in this study presents the problem of surface depletion of manganese since its pressure at 1230°K is 105greater than iron and 1020 greater than carbon. Since the existence of a volatile manganese carbide had been ruled out previously,' the high manganese pressure relative to iron and carbon insured that the only species leaving the effusion cell was manganese. Therefore, the effusing species required no analysis so that the manganese pressure was determined directly from the weight loss of the effusion cell. In order to detect small weight losses near the beginning of effusion, a vacuum microbalance was used to weigh the cell continually. These initial weight loss data allowed the rate of manganese effusion to be determined before the surface of the alloy became depleted in manganese. The apparatus used in this investigation is shown in Fig. 1. Temperature was measured using chro-

Jan 1, 1962

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By Selma Hermann

For the past century, the so-called aluminum bronzes have been assuming a role of ever-increasing importance in the metallurgical field. The last quarter of that century has marked many efforts to find alloying elements that would alleviate some of the undesirable qualities of the aluminum bronzes-for example, the heterogeneity of the alpha solid solution and the extreme hardness of the beta. Much of this work, however, has been rather haphazard-compositions and heat treatment are usually so much at variance as to make comparison impossible. It is the object of this research to study the effect of certain percentages of common alloying elements on aluminum bronzes of analogous compositions and heat treatments. It is hoped that the material gathered here will at least serve as a basis for further systematic study.

Jan 1, 1930

THE turn of the century was marked by the appearance of a series of greatly important pieces of research that became the foundations of modern physical metallurgy. It is, of course, some- what misleading to ascribe the growth of a science, or a branch of engineering, to the work of a few men, as it is to write history generally in terms of great men, for this approach neglects back- ground development, and tends to overemphasize the importance of immediately subsequent events; the correlative and steady growth of the basic sciences added to the resources of the new science of metals--developments in basic science .years later were to appear in their application to metal systems. Yet it is useful to emphasize the importance of these relatively few pieces of research. THE PHASE RULE The work of Willard Gibbs on heterogeneous equilibria, which included the derivation of the phase rule, was published obscurely in the journal of the Connecticut Academy.30 Unearthed by the German physical chemists (evidently by van der Waals, to use Ostwald's phrase, "aus dem staubigen Fundort"), its importance to the study of alloys was pointed out by Jüptner31 and by Le Chatelier; its application to polycomponent systems, and to metal systems in particular, was developed by Rijn van Alkemade (1893), by Le Chatelier;8a and especially by Roozeboom (1899-1900). The work of Raoult on the depression of the freezing point by solutes led to the study of the phenomenon in amalgams and shortly to metal systems. Work was done, by Roberts-Austen and others, on the initial freezing temperatures of binary alloys-the liquidi, data applicable to Raoult's work. Van't Hoff in 1890 had pointed out

Jan 1, 1948

BEING at the crossroads, metaphorically speaking, seldom has the advantages of the literal sense of the words. One seldom has precise knowledge of the existence of the metaphorical crossroads or forks in the road of life. A case in point is the Committee on Education of the Engineers' Council for Professional Development, which for twenty years has been accrediting the engineering curricula in the educational institutions of the United States. The committee is now at odds with itself and with the National Council of State Boards of Engineering Examiners over the accrediting of courses which in the opinion of many engineers are not strictly speaking engineering curricula at all. Such courses include: fire protection engineering, crystal engineering, nuclear engineering, and geological engineering. The crossroads might be placed arbitrarily somewhere between 1936 and 1938 when the committee first started accrediting curricula and included the first course in industrial engineering. Purists might argue that the committee first wandered from the straight and narrow when it recognized subdivision of engineering into the major branches of mining, metallurgical, civil, mechanical, electrical, and chemical engineering. Accrediting is certainly an important function because it provides a standard for engineering education and it should be done on a national basis by an unbiased group like the Education Committee of ECPD. Students, educational institutions, and industry derive great benefit from proper standards. The autonomous State Boards of Engineering Examiners have long accepted ECPD accreditation as evidence of the required academic training of engineers aspiring to licensing. But the State Boards today question the wisdom of applying the name engineer to graduates of some of the so-called fringe curricula. The Education Committee, having gone so far in accrediting some of them, has numerous applications pending for accreditation of similar curricula and even new courses never before accredited. Arguments against recognizing highly specialized engineering curricula are numerous. The Salary Stabilization Board has disallowed industrial engineering from classification as engineering for its purposes. A graduate of a specialized course in geological engineering at a school in the Southwest slanted heavily for practice in the petroleum industry might not be interchangeable with a graduate of a similarly designated curricula at one of the institutions in the North Central states where the emphasis might be on metallic. mineral deposits. Industry in general should not expect the universities to supply a degree in each of the specialized engineering classifications it might set up for purposes of salary or job designation. Having gone so far, it is easy to understand the difficulty of the Education Committee. ECPD might well call a moratorium for the purpose of taking stock of its position. If the present trend is allowed to continue, it is apparent that an engineering institution could be subdivided into a multiplicity of departments teaching specialized curricula resulting in a subordination of the basic concepts of engineering. Although the parallel of the medical profession is trite, it should be pointed out that degrees in medicine are not labelled by the numerous specialities practiced by doctors. For practical purposes the ECPD would do well to accept the fact that the crossroads have been overreached "and protect the engineering profession by coming up with minimum standards for an engineering curriculum.

Jan 1, 1952

By C. E. Taylor, L. V. Fegan

With on-stream electrical-resistance measurement as a basis, Bethlehem Steel developed a system for the completely automatic control of moisture in the feed to pelletizing. This system was later successfully adapted to the sintering process, with automatic control of moisture serving to maintain the air permeability required for effective burnthrough. Control of moisture content is an important factor in the agglomeration processes by which iron ores are converted into either pellets or sinter for use in blast furnace burdens. In both pelletizing and sintering the iron ore feed must be mixed with the proper amount of water so that capillary attraction and surface tension forces can be utilized to cause the ore particles to coalesce and form larger agglomerates. The success or failure of the entire pelletizing or sintering process depends on maintaining the proper moisture. Therefore, continuous automatic control of moisture is one of the conditions for the automation and optimum use of both pelletizing and sintering processes. In pelletizing, variation in moisture can cause ball size to change and is a common cause of cycling which results in a fluctuating feed to induration. Excessive moisture can cause lumps to form at the cutter bar and contributes to the formation of buildup on the green pellet screens. Green pellets with excess moisture deform and reduce bed permeability. In sintering, accurate control of moisture is also important because moisture must be within the limits that give the bed the required permeability for good burnthrough. In response to these problems, a moisture meter, based on the principle of electrical resistance measurement, was developed. This moisture meter has been a key factor in the development of systems for providing uniform feed of concentrates in most of Bethlehem's pelletizing and sintering plants. The automatic moisture control system for pelletizing was successfully plant-tested and resulted in the following: (1) Control of moisture in the green pellets to +0.2%. (2) Up to 50% reduction of bentonite consumption. (3) Control of unscreened green pellets so that 85% of the furnace product at Cornwall was within the size range of -5/8 +3/8 in. (4) Improved quality of product with a tumble test of 94 and a "Q" index of 90 as the result of feeding a consistently uniform feed to a shaft furnace. In sintering, where sinter-mix temperature change and variable feed could cause errors in moisture measurement, the system was designed to maintain the correct moisture under virtually all plant operating conditions. It was successfully plant-tested and is now in use in most of Bethlehem's sintering plants. The system achieves: (1) Control of moisture within the desired limits for optimum production. (2) Continuous measurement and control of moisture even with intermittent feeding of mix, so that attention by the operator is seldom required. The two automatic control systems provide smoother startup, minimize upsets and contribute to the consistent control of process variables in pelletizing and sintering. MOISTURE-CONTROL SYSTEM FOR PELLETIZING Fig. 1 shows the general arrangement of the system for automatic control of moisture in pelletizing.1 In this system a bin level controller, using a single probe which regulates filter speed, maintains a uniform low concentrate level in the bin.' The moisture meter, comprised of an analyzer and control components, continuously measures the moisture in the bed and adds water to adjust to the desired level. The meter is placed in an open-loop (feed-forward) control, i.e., water addition occurs downstream from the probes. Filter vacuum must be set so as to produce a filtercake moisture which is below the optimum for pelletizing. Bentonite is added after the

Jan 1, 1969

By Edgar C. Bain, William E. Griffiths

The results of an inquiry into the structural nature of some 70 iron alloys containing both nickel and chromium over a considerable range of concentration are briefly described in this paper. This study is a part of a comprehensive program of investigation into alloys involving chromium in progress at the Union Carbide and Carbon Research 1aboratories. All the compositions studied contained carbon in amount comparable to commercial alloys. The B Constituent In addition to locating the limits of composition for the three principal types of structure (polyhedral ferrite, martensite and austenite) and their combinations, certain other features of the system were observed. A hitherto undescribed brittle constituent (designated here as the "B constituent") was discovered. It is very hard, non-magnetic and forms in two modes from chrome-ferrite by recrystallization. It is the stable low-temperature condition for the equal-proportion chromium-iron materials containing less than 10 per cent. nickel. Although it partakes of the nature of an inter-metallic compound, yet it may exist over a considerable range of composition. It is non-existent above a temperalure zone, varying with composition, from 800° C. to 950° C., and heating above this critical temperature develops chrome ferrite persistent after average cooling rate; a few hours just below this temperature will develop the complicated brittle crystalline type. The B constituent, when found in the grain boundaries of alloys of lower chromium content, contributes a serious brittleness removable, however, by heating and cooling rapid enough to prevent its re-format'ion. By suitable means of precipitution, the hard B constituent can be made to strengthen the already stiff alloy matrix in the manner of submicro-scopic particles, as exemplified in duralumin or the Sykes iron-tungsten and iron-molybdenum alloys. A possible explanation is offered for the familiar brittleness developed in chrome iron at temperatures above about 475" C. and removable by

Jan 1, 1927