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By P. G. Shewmon

A novel technique for determining the surface energy (?) and its derivative with respect to orientation, (?') is described. Essentially it involves the 'floating" of a wedge on the substrate, said wedge being made of a material which is not wet or only slightly wet by the substrate, i. e., as a greased needle "floats" on water. A thermodynamic analysis of a system in which the wedge is supported entirely by surface energy is given. If the original suyface is not at a cusp orientation, the surface tension is directly measurable from the groove angle formed. If the original surface is at a cusp orientation, there may or may not be a groove depending on the relative value of ?' and the weight of the wedge. Experiments primarily on copper and silver showed that sapphire, quartz and refractory metal wedges were wet while graphite wedges were not. The technique was demonstrated to work using graphite wedges, but the results obtained were not as eccurate as those obtained by other workers using the wire-creep experiments. It is concluded that the technique might prove most useful with non-metals where ?' is large and filament creep experiments would be quite difficult. If an absolute value of the surface free energy (?) of a metal is to be determined, the most reliable methods used to date measure an average over the various orientations exposed on a polycrystalline sample. For example, ? for silver, gold, and copper have been measured by determining the force required to just keep a thin wire,' or foil,' specimen from contracting under the influence of ?. Herring 3 has predicted and experiment confirms, that the sensitivity of this method is inversely proportional to the grain size.' Thus it cannot be used to measure ? for a particular orientation by using a foil single crystal or a very coarse-grained specimen. An accurate value if ? for tungsten averaged over a range of orientations has been determined using a field emission technique. The same techniques cannot or have not been used to measure ? for non-metallic solids, and as a result the values available are much less accurate.4 This Paper resents a means of making an absolute determination of ? for a particular surface orientation on any solid, as long as the given surface orientation does not break up into other orientations during an anneal. Experimentally ? is found to vary with orientation and at a few low index orientations it is found to have a cusped minimum, i.e., the derivative of ? with respect to the orientation of the surface changes discontinuously at the low index orientation, see Fig. 1. The slope of a plot of ? vs orientation (herein designated ?') is called the torque on the surface, since it tends to rotate the exposed surface toward the low index orientation, or if the surface is at the cusp orientation it opposes any force tending to rotate the surface out of the low index orientation. The ratio ?'/? has been determined for a few metals, but in cases where this ratio is high there is presently no means of determining either ?'/? or the absolute value of ?' for the orientations present on an annealed surface. The technique discussed herein also provides a means of determining an absolute value of ?' for those orientations which deviate only infinitesimally from a cusp orientation. It should work best on surfaces where ?'/? is large; that is, for cases where no other technique is available for measuring ?'. Aside from trying to learn more about surfaces through measuring ? and ?', the primary reason for wanting values of ? or ?' is to study adsorption. From measurements of the variation of ? for a particular orientation with the concentration of an impurity, one can obtain the number of impurity atoms adsorbed per unit area (Ti) on that orientation using the Gibbs adsorption equation.' where µi is the chemical potential of the adsorbed impurity. Thus, if absolute values of ? could be obtained for the free surface of a given surface orientation as a function of µi, ri could be determined for the given orientation. Furthermore, by equilibrating a grain boundary with the given surface at various values of ki, one could also determine ri for the grain boundary. Similarly Robertson 6 has pointed out that if y is taken to be a continuous function of and µi, then a2 ?/a @a µ2 = a2 ?/a pi a +. Thus, at all orientations away from cusps the following equation holds From a measurement of ?' vs ki, it is thus possible

Jan 1, 1963

By R. G. Davies

The activation energy for steady state creep above -500°C is observed to be independent of the applied stress although it varies from -67 kcal per mole at 2 at. pct Si to -100 kcal per mole at 11 at. pct Si due to changes in crystallographic order. The magnitude of the activation energy, by comparison with Fe-A1 alloys, indicates FeSi type of order in certain alloys. X-ray results confirmed the presence of FeSi type of order. It is proposed that dislocation climb is the rate controlling mechanism for all the alloys. It has been demonstrated that when a diffusion mechanism is the rate controlling process, the formation of a superlattice in brass,1 Fe3A1,2 Ni3Fe,3-5 and Feco6 1) increases the creep resistance, and 2) increases the activation energy for steady state creep. Furthermore, a study of creep in Fe-15 to 20 at. pct A1 alloys7 has revealed that as the alloy composition approaches the long-range order field, there is an increase in the activation energy for steady state creep which is thought to be due to an increase in short range order. Fe-A1 and Fe-Si alloys are similar in that they both form the DO3 superlattice in which aluminum or silicon atoms have only iron atoms as first and second nearest neighbors. There are, however, two important differences between the alloy systems: 1) The superlattice formation at -350°C commences at -10 at. pct si8 as compared to -20 at. pct Al,9 and 2) Fe-A1 alloys form a FeAl (B2 type) super-lattice where aluminum atoms have all iron first nearest neighbors even at 22 at. pct Al, but so far no similar FeSi superlattice has been observed. With the similarity between Fe-A1 and Fe-Si alloys in mind, alloys of iron with 2 to 11 at. pct Si were examined for variations with composition of the activation energy for steady state creep and of creep strength. The temperature range of greatest interest was above 1/2 TM (TM is the absolute melting temperature) where it is usually observed that diffusion is the rate controlling process. A subsidiary X-ray investigation of the Fe-Si system was undertaken in an attempt to define the position of the order-disorder boundary as a function of cooling rate. EXPERIMENTAL DETAILS a) Creep. Specimens whose gage length was 1.5 in. and with a cross-section 0.04 by 0.08 in. were strained in tension by a lever-arm arrangement, and the load was adjusted between each creep test to maintain constant stress. The apparatus and mode of operation have been fully described in a previous publication.7 As each test produced a creep strain of 0.25 pct, the variation in stress during the test was negligible. Creep strain was measured at the end of one of the alloy steel grips by a displacement transducer with the out-of-balance potential being recorded on a variable speed recorder. The full-scale deflection of the recorder could be varied in steps to give limits of sensitivity of between 0.1 and 0.001 pct creep strain. The alloys, Table I, were made available by the Metallurgical Department, National Physical Laboratory (N.P.L.), england,10 and by the Research Department, General Electric Co. (G.E.), Schenectady, N.Y. They were hot worked at -850°C, warm worked at 550° to 650°C, and recrystallized in vacuum at -750°C to give a grain diameter of -0.1 mm. All the alloys had a very low impurity content; those from the N.P.L., for which a complete analysis is available,&apos;&apos; show carbon less than 0.026 pct, manganese less than 0.006 pct, and oxygen plus nitrogen less than 0.0024 pct. b) X-ray Procedure. A General Electric XRD-5 X-ray set with a focussing lithium fluoride mono-chromator in the diffracted beam, and a pulse height analyzer to eliminate harmonic wavelengths of the cobalt radiation, was used to investigate the structure of several very fine grained (grain diameter <.01 mm) Fe-Si alloys after the following heat treatments: 1) Quenched from 700°C, 2) slow cooled from 650°C (-40°C per hr), and 3) very slowly cooled from 400° to 100°C (10°C per hr with a 24 hr anneal every 100°C). The method of obtaining the diffraction pattern over the range of 20 from 15 to 45 deg was to count for at least 100 sec every l/3 deg with a slit subtending 1 deg in 20 at the focus; the probable counting error was less than 2 pct.

Jan 1, 1963

By D. W. Loucks

There is plenty of evidence to indi-cate that at least one of man&apos;s chief interests in life is to make himself as comfortable as possible. If you doubt this, just watch the fellow next to you for the next half hour trying to find the most comfortable position that a hard chair has to offer. Comfort, however, does not always mean an easy chair. To some, it may mean a wealth of money; to another, freedom from worry. But to most of us, it means first of all a comfortable atmosphere in which to live, and to a great many of us it probably also means freedom from that annoying task of firing the furnace. Today more than ever before. automatic heat is one improvement that is placed high on everyone&apos;s list. Perhaps this is because automatic heating is becoming relatively cheaper. Perhaps it is because of a good publicity campaign on the part of the oil and gas men or maybe it is just that we are getting lazier day by day. At any rate, almost every issue of Better Homes and Gardens, House Beautiful, or your other favorite home magazine carries an article extolling the virtues of this or that automatic heating system. If I were to ask you to name the first thing that came to your mind when I said automatic heat, you would prob-ably say either gas furnace or oil burner. Or if you had just been studying heating systems, you might possibly say heat pump. But chances are you would not mention anything about coal, and yet coal is the most common source of the greatest automatic heat of them all. I say this because coal is the fuel used almost universally by the district heating industry in producing and delivering to certain heavily populated areas heat ready to use at the touch of a valve or the click of a thermostat. Although the industry is over a half century old, it has not experienced the widespread development of other utility industries because of certain limitations which I believe you will realize from the next few minutes discussion. District Heating Operations We may define district heating as any operation where two or more buildings are heated from a central heating plant. The method of heat transfer may be hot water or in some cases warm air, but generally the medium of heat transfer is steam. So universally is steam used that the industry is frequently referred to as the district steam industry. The Allegheny County Steam Heating Co. which operates the district heating system in downtown Pittsburgh is a subsidiary of the Du-quesne Light Co. Although organized in 1912 primarily as a means of securing the electric load of downtown buildings, the service has now become so valuable and so popular that it is no longer considered a necessary adjunct to the electric business but rather a separate business standing on its own feet. Fig 1 shows the layout of the plants and distribution system of downtown Pittsburgh. Two generating plants, one known as the Stanwix and the other as Twelfth Street, supply the area. Each has two boilers with capacity totaling 1,350,000 lb per hour. The Stanwix Plant is supplied coal by truck. The coal is pulverized at the plant and burned as powdered fuel. Coal is supplied to the Twelfth Street Plant also by truck but the boilers arc stoker fired. Over 1 1/2 miles of tunnel house a portion of our main lines, but it requires over twelve miles of pipeline, ranging in size from 32 down to 1 in. in diameter, to supply all our customers. The distribution system consists of two systems in a sense, one high and one low pressure with certain interconnections between the two. Our high pressure system supplies steam up to 125 Ib to some but not all customers, while the low pressure system operates in the range of 10 to 20 psi. Note that the two plants are tied together through large steam mains and that the system to some extent is a loop system, making it possible to have a portion of the line shut, down without interrupting service to any customer. Fig 2 conveys a picture of the extent to which steam service is used in the downtown triangle. The black area indicates the buildings which now use district steam. The dotted area indi-

Jan 1, 1950

By Glenn S. Wyman

CHUQUICAMATA, located in northern Chile in the Province of Antofagasta, is on the western slope of the Andes at an elevation of 9500 ft. Because of its position on the eastern edge of the Atacama Desert, the climate is extremely arid with practically no precipitation, either rain or snow. All primary blasting in the open-pit mine at Chuquicamata is done by the churn drill, blasthole method. Since 1915, when the first tonnages of importance were removed from the open pit, there have been many changes in the blasting practice, but no clear-cut rules of method and procedure have been devised for application to the mine as a whole. One general fact stands out: both the ore and waste rock at Chuquicamata are difficult to break satisfactorily for the most efficient operation of power shovels. Numerous experiments have been made in an effort to improve the breakage and thereby increase the shovel efficiency. Holes of different diameter have been drilled, the length of toe and spacing of holes have been varied, and several types of explosives have been used. Early blasting was done by the tunnel method. The banks were high, generally 30 m, requiring the use of large charges of black powder, detonated by electric blasting caps. Large tonnages were broken at comparatively low cost, but the method left such a large proportion of oversize material for secondary blasting that satisfactory shovel operation was practically impossible. Railroad-type steam and electric shovels then in service proved unequal to the task of efficiently handling the large proportion of oversize material produced. The clean-up of high banks proved to be dangerous and expensive as large quantities of explosive were consumed in dressing these banks, and from time to time the shovels were damaged by rock slides. As early as 1923 the high benches were divided, and a standard height of 12 m was selected for the development of new benches. The recently acquired Bucyrus-Erie 550-B shovel, with its greater radius of operation compared to the Bucyrus-Erie 320-B formerly used for bench development, allowed the bench height to be increased to 16 m. Churn drill, blasthole shooting proved to be successful, and tunnel blasts were limited to certain locations where development existed or natural ground conditions made the method more attractive than the use of churn drill holes. Liquid oxygen explosive and black powder were used along with dynamite of various grades in blast-hole loading up to early 1937. Liquid oxygen and black powder were discontinued because they were more difficult to handle due to their sensitivity to fire or sparks in the extremely dry climate. At present ammonium nitrate dynamite is favored because of its superior handling qualities and its adaptability to the dry condition found in 90 pct of the mine. In wet holes, which are found only in the lowest bench of the pit and account for the remaining 10 pct of the ground to be broken, Nitramon in 8x24-in. cans, or ammonium nitrate dynamite packed in 8x24-in. paper cartridges, is being used. This latter explosive, which is protected by a special antiwetting agent that makes the cartridges resistant to water for about 24 hr, currently is considered the best available for the work and is preferred over Nitramon. Early churn drill hole shots detonated by electric blasting caps, one in each hole, gave trouble because of misfires caused by the improper balance of resistance in the electrical circuits. Primarily, it was of vital importance to effect an absolute balance of resistance in these circuits, the undertaking and completion of which invariably caused delays in the shooting schedule. Misfires resulting from the improper balance of electrical circuits, or from any other cause, were extremely hazardous, since holes had to be unloaded or fired by the insertion of another detonator. The advent of cordeau, later followed by primacord, corrected this particular difficulty and therefore reduced the possibility of missed holes. After much experimentation, the blasting practice evolved into single row, multihole shots, with the holes spaced 4.5 to 5 m center to center in a row 7.5 to 8 m back from the toe. Sucti shots were fired from either end by electric blasting caps attached to the main trunk lines of cordeau or primacord. The detonating speed of cordeau or primacord gave the practical effect of firing all holes instantaneously. Double row and multirow blasts, fired instantaneously with cordeau or primacord, proved to be unsatisfactory in the type of rock found at Chuquica-

Jan 1, 1953

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur&apos; and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen&apos; and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,&apos;&apos;&apos; who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide

By Benny Langston, Frank M. Stephens

Although little information is available concerning small-scale equipment for dust collection in laboratories, it is possible to adapt standard equipment for laboratory use. Dust from laboratory processes may be collected by cyclone separators, filters, electrostatic separators, scrubbers, and settling chambers. IN recent years much attention has been given to recovery, treatment, and disposal of dusts discharged into the atmosphere from operations of industry. considerable data has been accumulated on both operation and design of dust-collector equipment for commercial installations. On the other hand, there is almost no published data on design and construction of small-scale equipment to handle dust problems that arise in the ore-dressing laboratory. Dust-collection equipment such as multiclones, single-cyclones, scrubbers, chemical and mechanical filters, settling chambers, and electrostatic separators has proved its efficiency for collecting dust in industry. In the laboratory, however, the engineer is faced with the problem of collecting small quantities of dust, inexpensively, without diverting the major effort from the metallurgical problem to the problem of collecting dust produced by the process. For most applications standard dust-collection equipment is too large for use in the laboratory; however, for control of dust in large working areas it is often possible to use a standard dust collector, such as an air filter, with branch ducts to eliminate a health hazard. For example, the well-furnished sample-preparation room containing small jaw crushers, rolls, and pulverizers, in addition to the riffles and screens necessary for preparation of samples, presents a perennial source of dust. The authors&apos; experience has shown that a combination system consisting of overhead branch ducts to the individual equipment and floor ducts with grills, where applicable, connected to a central dust collector effectively removes dust generated in preparation of samples. Fig. 1 is a sketch of a downdraft dust-collector for table installation. Similar systems can be built with floor grids. For portable equipment such as laboratory vibrating screens this type of installation with a steel grill to support the heavy load is reasonably efficient. Overhead branch ducts to individual crushing and grinding equipment, although efficient, must be carefully controlled by dampers to prevent excess loss or a change in the composition of the sample. Change in sample composition can result from excess velocity, which causes selective removal of constituents of low specific gravity. Fig. 2&apos; shows the theoretical effect of terminal velocity on spherical particles of different specific gravities in air and water under action of gravity. Fig. 3 shows the effect of air velocity on composition of CaCO, coal mixtures. Although the entrainment of dust particles in a moving air stream is the basic mechanism by which all dust-collection equipment functions, usually intake velocity of the dust-collection system must be controlled to prevent loss of part of the sample. As an example of what may happen when excess velocities are used, a mixture of 50 pct coal and 50 pct limestone was crushed to —10 mesh and fed to a pulverizer equipped with an overhead dust-collection system. Fig. 4 shows the overhead dust-collection equipment used in this test. The pulverizer was set to give a product 95 pct —100 mesh in two stages. Velocity of air passing over the lip of the pulverizer was measured with an anemometer. After grinding, the finished product was analyzed to show the amount of calcium carbonate present. Fig. 3 shows graphically the increase in calcium carbonate as velocity through the dust-collection duct was increased. These data show that at a velocity of 1 ft per sec little if any of the coal was entrained by the overhead draft. At the maximum velocity, about 6.5 ft per sec, approximately 7 pct more coal was entrained than calcium carbonate. From an operating standpoint, this problem can be remedied easily by dampering the line to control velocity. The lowest velocity commensurate with satisfactory dust control should be used to prevent excess loss and, in some cases, selective dust loss. Collection of Dust in Laboratory Processes As in industry, the engineer desires to collect efficiently the dust produced by processes being investigated on a laboratory scale. However, in the collection of laboratory dusts he is faced with two additional problems: 1—The volumes of gas and the quantity of dust that must be recovered are small when compared with the capacity of standard dust-collector equipment, which must be scaled down in design except for collection of dust from large pilot-plant operations. 2—In addition, because of the variety of problems studied in the process laboratory, the engineer cannot design today a dust collector that will meet the conditions imposed by the processes of tomorrow. Sometimes, therefore, he must compromise collection efficiency to minimize the cost of fabrication and the amount of time diverted from the metallurgical to the dust-control problem. For collection of dust from laboratory processes a cyclone separator, filters, electrostatic separators, scrubbers, and settling chambers can usually be adapted for small-scale operations. The following

Jan 1, 1955

By C. B. Sclar and

A graphical solution is presented for the equation v =v &-cU where vb is the volume of liquid b of density 6 that must be added to liquid a of volume va and density d, in order to obtain a heavy-liquid solution of preferred density dm for mineral fractionation. The equation is valid only for pairs of liquids whose volumes are additive, but empirical density-composi-tion data show that this condition is met over wide compositional ranges by all of the heavy solutions that are commonly used for mineralogical analysis. The chart is a nomograph which consists of two horizontal volume scales ad a vertical density scale arranged so that one volume scale occurs on each side of the density scale. All the scales are linear. For two liquids of density d, and &, respectively, each volume scale has an independent level on the density scale, ad the graphical solution for vb on the nomograph is obtained by construction of one straight line. The chart can be prepared easily to cover any density range with any desired accuracy by proper selection of the scales. Heavy-liquid separation of particulate samples is an indispensable analytical procedure in the mineralogical and mineral-process ing laboratory. Heavy liquids may be used 1) to isolate specific minerals in the form of high purity products or to fractionate samples into several products with density limits for petrographic, chemical, spectrographic, and X-ray diffraction analysis,&apos;-&apos; 2) to determine the density of minerals,&apos;-l4 3) to facilitate the recognition and identification of optically similar associated minerals,15 and 4) to determine quantitatively the degree of liberation of ore minerals in ores and mill products at various limiting sizes." The preparation and recovery of heavy liquids suitable for mineralogical analysis are discussed fully in the literature and operational procedures and special equipment for heavy-liquid separation are described in numerous references.&apos;747837&apos; 13,18,25-42 Useful tabulations of heavy liquids for mineralogical analysis are given by Tickell, Mil-ner,&apos; Twenhofel and Tyler,&apos; and Lange and a very complete up-to-date list of minerals arranged according to increasing density is given by Mursky and Thompson. USEFULNESS OF THE DENSITY CHART For any particulate sample, the limiting densities selected for its fractionation by means of heavy- liquid separation depend on the respective densities of the constituent minerals and the specific objectives of the separation. In many instances, the densities of readily available and practicable heavy liquids do not coincide with those that are required, and suitable liquids of the proper density are obtained by dilution with miscible liquids. In the general case, one may wish to mix either a pure liquid (A) or a solution of two miscible liquids (AP,,) of known density with either a pure liquid (B) or a different solution of the two miscible liquids (A,B,) of higher or lower density in order to obtain a final liquid of the preferred density. In conventional practice, the latter is reached empirically by trial-and-error addition of increments of one liquid to the other. The density of the final solution may be determined either by accurately weighing a known volume of the final liquid,&apos;&apos; 532;4;40, or by means of I)a Westphal balance, 2)a hydrometer, a refractometer in the case of binary liquid systems for which density-refractive index data are available,15 4) natural or synthetic .indicators of known density, a pycno-meter. Like all trial-and-error methods, these procedures are time consuming and many require special equipment which may not be available, The purpose of this paper is to show that the volume of a liquid of known density which is to be added to another liquid of known volume and density in order to obtain a solution with an intermediate preferred density may be determined rapidly and accurately by a graphical method provided that the two liquids form ideal or quasi-ideal solutions whose volumes are additive. Empirical data47&apos;8~&apos;8~4B&apos;49 show that solutions prepared from pairs of miscible

Jan 1, 1961

E. C. Pechin, Buchanan, Va.: I am sorry to see the table appended to Mr. Chase&apos;s excellent paper. In the discussion at the same meeting, on "Notes on a Southern Coal-Washing Plant," Prof. Phillips very properly says: " There is no use in giving an analysis as representing a coal when it does not do so. It gives a wrong impression of the conditions under which business is conducted." The same may be said about ores. I have no personal knowledge of the ores in many of the localities given in Mr. Chase&apos;s table; but if these are to be judged by what is positively known of the Cranberry ores, the analyses are grossly misleading. The furnace-shipments from Cranberry have rarely reached 44 per cent. of iron, and any such percentage as 58 or 66 or 68 can only have come from hand-picked specimens. Indeed, with any such percentages, Mr. Chase&apos;s paper would have been superfluous, because concentration would be unnecessary. Besides, the paper itself (page 553) gives the fact that the Cranberry average is 42 to 43 per cent. Why should a table be appended, contradicting this statement of the text ? Let us always have the exact conditions under which business may be conducted. "Boom" and business analyses are widely different.

Jan 1, 1896

By C. Wert, G. Mah

A relaxation peak thought to be due to the presence of C-C pairs in cobalt has been observed. It exists both above 420"C, where cobalt has the fcc structure, and below 420"C, where cobalt has the hcp structure at equilibrium. The effect is thought, however, to be caused by motion of C-C pairs in the fcc phase in both instances; enough retained fcc phase was deduced to be present at temperatures below 420°C to make the phenomenon possible. Measurements of the aniso-tropy of the effect in single crystals of various orientations of fcc phase showed the effect to have a maximum value in longitudinal strain for a [loo] crystal and a minimum value for a [Ill] crystal. This observation seems to rule out the possibility of (110) nn pairs being responsible for the effect. From measurements of the strength of the relaxation in the alloys, we reach the conclusion that both the binding energy of the pairs and the specific relaxation per pair are smaller than corresponding quantities for interstitial pairs in bcc metals. DETERMINATION of the details of atom placement of small atoms such as carbon, nitrogen, oxygen, and hydrogen in metals has been a difficult problem. In certain alloys such as martensite extensive departure from random placement of the interstitials can be deduced from X-ray diffraction off the atoms of the host metal, but such diffraction techniques are of small help for small departures from randomness. A technique which does offer promise in the latter instance is the anelasticity of these interstitial alloys. Most previous investigations using this property have utilized alloys in which the solvent is one of the bcc metals, alloys such as These studies have been interpreted to show that an interaction exists between interstitials which causes them to form clusters in more than random numbers; the binding energy of interstitials in such clusters has been deduced to be about 0.1 ev per atom (for small clusters of size two to four atoms). Similar investigations have been carried out on close-packed solvent metals, Ni-C by and Diamond and Ag-O by Papazian.8- In both of these svstems. no relaxation of the singly dissolved interstitial is expected, so an-elastic behavior of the interstitials must be caused by their association in some cluster or complex of non-cubic symmetry. Since relaxations in these alloys were observed to have a strength which varied about as the square of the interstitial concentration, the effect was deduced to be caused predominately by motion of i-i pairs in the crystal. A striking difference is observed in relaxation strength of interstitial alloys between the bcc and fcc systems. The specific effect per interstitial atom is much larger for the alloys in the bcc crystals than for those in fcc crystals. Comparing clusters of size two in the Nb-O system4 and the Ni-C system,7 one finds the magnitude of the anelastic effect per interstitial atom in the former to be some 100 times greater than that in the latter. Such a difference in relaxation strength might be caused by a difference in concentration of the pairs (this means a higher binding energy in the bcc crystals). It might also be caused by a large difference in shape factor of the elastic strain field about the pairs between the two cases (a much more noncubic shape factor would be required for the bcc crystals). This investigation was undertaken to examine the possibility of C-C pair formation in alloys of cobalt and carbon using anelastic effects. Since cobalt has both fcc and hep phases, it seemed to offer the chance that measurements over a range of frequency might permit comparison of properties of pairs in the two crystal types. Although this goal was not reached, several significant facts were deduced from the observations. 1) An anelastic phenomenon believed to be associated with the presence of C-C pairs in cobalt exists. It has many features in common with that observed in nickel. 2) The effect is thought to be caused by pair motion in the fcc phase. 3) Calculations of the relaxation strength A, which includes as a parameter the product of the pair concentration, C, and the square of the shape factor &apos;, show that this parameter is much smaller in the CO-C alloy system than in the interstitial alloys in the bcc systems. 4) From this finding, we reach the conclusion that both the binding energy of C-C pairs in cobalt and the specific relaxation strength per pair are small compared to corresponding values for such pairs in the bcc systems. 5) The crystalline anisotropy of the effect permits the identification of reasonable geometrical models of close C-C pairs. I) EXPERIMENTAL PROCEDURE A) Method of Measurement. The anelastic measurements-—all of which were constant frequency measurements of internal friction—were designed to study the expected phenomenon in both the hcp and fcc structures in cobalt. Knowledge of similar measurements in Ni-C alloys led us to believe that the damping peak should occur below the transformation temperature for frequencies near 1 cps and above for frequencies near 100 kcps. This surmise was correct. The low-frequency measurements were made on wire specimens using a vacuum torsion pendulum; the damping peak was found at about 2&apos;70°C at a frequency of 1 cps. Because of large superimposed damping of magnetic origin at this temperature, a longitudinal magnetic field of about 1500 oe was applied to the

Jan 1, 1969

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,&apos;-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4&apos;5&apos;7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller&apos;s arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3&apos;" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?&apos; precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.&apos; These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.&apos; In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y&apos; intermediate precipitate, to- gether with some G.P. zones,&apos; which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800&apos; to 1260°F (425&apos; to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800&apos; to 1000°F (425&apos; to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800&apos; to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590&apos; to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800&apos; to 1000°F (425&apos; to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,&apos; representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum&apos; for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,&apos; Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal&apos; and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By J. C. Karcher

GEOPHYSICAL methods have been more extensively applied to prospecting for oil during 1936 than at any previous time. Their use has been extended to include al- most every oil and gas producing area in the United States. More than ten magnetometer parties, more than nine gravimeter parties, more than five electrical surveying crews, more than fifty torsion balance parties, more than two hundred seismic reflection parties, and several refraction parties were- operating in the United States throughout the year. A tendency has been noted to abandon the use of the pendulum for geophysical prospecting in the oil fields and to increase the use of the

Jan 1, 1937

By Peter R. Drummond

THE final casting of refined copper has been re-J- stricted for generations by the following sequence of operations: Filling the reverberatory furnace, melting, skimming, blowing or flapping, and poling. The hoped-for 24 hr cycle, producing 300 tons or more, has been taken up largely with the necessary bat time-consuming tasks of cleaning the bath, sulphur elimination, and in turn removal of excess oxygen to produce tough-pitch copper. Incidental to comparatively slow melting under combustion gases, copper oxides react with the furnace lining, and the slag so-formed must be completely recycled. The three-phase arc furnace has eliminated some of the cycle stages, and telescoped the remainder into a continuous operation. Electrical energy, supplied to graphite electrodes enclosed in high grade refractories, rapidly melts copper cathodes and sustains a stream of metal, containing approximately 0.01 pct oxygen, without contamination from fuel. The arc was struck on the first large electric furnace for melting copper in the United States on April 13, 1949. The earliest use of this type of furnace was at Copper Cliff, Ont., in 1936, and an admirable description of their installation has been published? Copper, melted in the Baltimore furnace, is used to cast billets, and the installation differs somewhat from the Canadian, as will be described. The arc furnace is a heavy-duty, three-phase furnace, holding 50 tons, the general outline of which appears on Fig. 1. The steel shell is 15 ft ID with a bottom radius of 14 ft 2 in. The roof, separate and distinct from the body, consists of a 15-ft water-cooled, cast-steel ring of the same outside diameter as the furnace. The center line of the furnace lies 9 ft 6 in. from that of the trunnions, permitting a 5" backward tilt for skimming, and a 40" maximum nose tilt forward for complete draining. Normally, the furnace overflows by displacement, and the use of the forward tilt arrangement is restricted to covering charging delays. The charging slot, 3 ft 8 in. x 5 in., lies on the north center line, the tap hole on the south, and the 30x30 in. skim door 45" to the west of the slot. The original 20-in. graphite electrodes were replaced with 14 in. in December 1949. Three conventional direct current winch drives, governed by electrical controls, position each electrode which has individual mast supports and counterweights. An independent circulation supplies cooling water for the electrode glands, the roof ring, charge slot, and the skim door frame. Arc Furnace Refractories Hearth: Fused-in monolithic bottoms had been used in copper arc furnaces, installed prior to April 1949. These consisted of thin layers of periclase, successively fused in place over preliminary brick courses. Heat was obtained from the arc, using a T-like arrangement of broken electrodes resting directly on the periclase to be fused. The operation, taking weeks to perform, was very expensive. The chemically-bonded magnesite-brick bottom, installed at Baltimore, was the first of its kind and a radical departure from previous practice. It consists of a 1 to 6-in. layer of castable refractory laid on the steel shell, modifying it to a 12 ft 2 in. bottom radius. Two courses of 9x2 % -in. fireclay straights and keys follow. The third course is made of 9-in. magnesite blocks of special shape to form circles of an inverted arch. It was started by a four piece keystone with skew-backs forming the outer course. The fourth course also started on a central keystone, or button, of four 90" segments, 12 in. diam x 13 Vz in. deep, and continued with 13%-in. blocks. Skewbacks at the shell completed the course to produce a horizontal surface for the side walls with a single course of No. 2 arch fireclay against the steel. Dry chrome-magnesite cement was brushed over each course after laying, and a 1-in. expansion space between the brick and the shell was filled with the same mixture. The total bottom thickness, excluding the castable material, was 5 in. of clay plus 22% in. of chemically-bonded magnesite. Tap Hole: A 5-in. OD and 3-in. ID silicon-carbide tube constitutes the tap hole and is set tangential to the upper course of the furnace bottom. Molten metal fills the tube when the furnace is level and filled to capacity. Side Walls: The lining, against the shell, consists of a 9x4Y2x3 in. soldier course of fireclay, using straights and No. 1 arches to turn the circles. A second soldier course of 9x4&apos;/2x2&apos;/2-in. fireclay was laid in a somewhat similar fashion. Three courses of 13Y2x6x3 in. and 9x6~3 in. of final magnesite, laid flat, completed the lining, using Nos. 1 and 2 keys to turn the circles. Cardboard spacers were placed between every two bricks in horizontal courses, and a thin coat of chrome-magnesite cement filled the joints between the firebrick and magnesite. A sprung-arch spanned the skim door with jambs of suitable magnesite shapes. Charge Slot: The slot is 3 ft 8 in. wide x 5 in. high. A silicon-carbide sill of special shapes has a 30" slope to allow cathodes to slide easily into the bath. The original arch was flat, and composed of Nos. 1 and 2 wedge magnesite with a 6-ft radius. It projected 5 in. over the sill, and, being a flat arch, gave an 18 15/16-in. opening between the inner edge and the metal line. The whole assembly was later raised 9 in., and the flat arch replaced with an arch, the lower edge of which maintained the 5-in, width from the outer to inner edges as shown in Fig. 2. A water-cooled, cast-copper jacket protects the steel shell behind the slot.

Jan 1, 1952