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By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By Ben E. Lindsly

PetRoleum engineers generally are familiar with the investigations of Dow and Reistle,1 Beecher and Parkhurst,2 and Dow and Calkin3 relative to the solubility of natural gas in crude oil. Since the publication of the results of those investigations and the work of Mills and Heithecker,4 little additional knowledge on this interesting and important subject has appeared in the petroleum engineering literature. The reports of Beecher and Parkhurst and Dow and Calkin agree substantially. The data from both investigations showed that, under the conditions of the tests, the solubility of natural gas in crude oil increased in direct proportion to the pressure at which the gas was put into solution, and the solubility decreased to a considerable extent with increased temperature. These facts, and others relating to the changes in viscosity, surface tension and specific gravity of the crude caused by the solution of gas in the oil, have been given due consideration in the petroleum industry, and the recognition of these facts has resulted in a great improvement in the technique of producing oil. However, in these first experiments, various grades and types of weathered crude oil were contacted at various pressures up to 500 lb. per sq. in. gage with gases deficient to a considerable degree in the heavier hydrocarbons, as compared with the gas that was originally in solution in the oil in its natural underground reservoir. The amount of dissolved gas that was liberated upon reducing the pressure to 1 atm. was measured. For these reasons, the complete significance of the effect of dissolved gases in crude oil, as it occurs in nature, cannot be determined directly from the data obtained under the conditions of the tests as described.

Jan 1, 1931

George W. Maynard, New York, N. Y.:—It is well known that there are many magnetite-mines of which the ore is too low-grade for direct use in the blast-furnace. For carrying out the sintering process, the preliminary step, in the case of magnetites, is the separation of the ore from the gangue by magnetic concentration. The resulting fine-grain product is very objectionable in the blast-furnace, and when used must be a very small percentage of the charge. The sintering process has saved the situation by furnishing a product which is absolutely ideal on account of its cellular structure. (In reply to questions by W. J. Tudor, and Joseph W. Richards, the following additional information was given by Dr. Maynard.) The percentage of iron in the product is determined entirely by the degree of concentration of the raw material and is practically not increased by the sintering operation. The magnetic concentrates at Port Henry and at the Benson and one or two other mines contain from 65 to 67 per cent. of metallic iron. The cost of sintering is from 39 to 41 cents per ton of product, including superintendence, depreciation, and repairs. The itemized figures are about as follows : Mixing (including labor), 24; power, 9; ignition, 5; repairs, 3; total, 41 cents. Prof. J. W. Richards, South Bethlehem, Pa.:—From a metallurgical standpoint I question the accuracy of the statement on p. 374: " C.—An increased reducibility of the iron so treated. (This has been conservatively estimated as 5 per cent. better than the best available ore.)" It seems to me that when a material is' sintered in this way, the constituents present, as lime, silica, and alumina, have a chance to form a compound with the iron oxide; that such a compound, if formed before the material goes into the blast-

Jan 1, 1913

By Holbrook G. Botset

It is possible by means of the electrolytic model to simulate water-flooding or gas recycling systems involving input and output wells, and also the encroachment of a natural water drive. The results are obtained pic-torially, and by simple measurements and calculations the percentage of recovery is obtained qualitatively as a function of the total input. Introduction The increased demand for petroleum products, together with the decline in discovery rate and the higher cost of recovery as deeper formations are brought into production, has stimulated interest in methods for studying and predicting efficiencies of various production programs. Among methods Of recovery that have become of increased significance recently are gas recycling in condensate fields and secondary recovery by water-flooding. The electrolytic model is a useful device for studying such methods in the laboratory, at least in a qualitative way. The original experiments with electrolytic models and the development of their application to the study of secondary reCoverY problems were published in 1933. 1,2,3 Subsequently other investigators continued the development and modification of the bait method, with resultant improvements and extension of its applications.4-7 The method and equipment to be described here are thought to represent still further improvement in the results obtainable, with increased validity in their application to field problems. Sand OF Principles of Operation The underlying theory of the operation of the model is given in references I, 2 and 3. However, a brief statement of principles involved is given herewith. The applicability of the model is based on the fact that Ohm's law and d'Arcy's law are exactly analogous; whence, electrical flow through a conducting medium may be used to simulate homogeneous fluid flow through a permeable medium. If two electrodes are placed in a conducting (ionized) solution and connected to the positive and negative terminals of a source of direct current, the positive ions of the solution will move toward the negative terminal, Since the velocity of an ion in an electrolytic medium is proportional to the electrical gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the motion of the ions in the potential field will be the same as the motion of fluid particles in a porous medium if the positive and negative terminals (input and output wells) and boundary conditions are made equivalent in shape and distribution. In order for the analogy to hold exactly, the sand must be assumed to have uniform porosity and permeability and the input

Jan 1, 1946

By Holbrook G. Botset

It is possible by means of the electrolytic model to simulate water-flooding or gas recycling systems involving input and output wells, and also the encroachment of a natural water drive. The results are obtained pic-torially, and by simple measurements and calculations the percentage of recovery is obtained qualitatively as a function of the total input. Introduction The increased demand for petroleum products, together with the decline in discovery rate and the higher cost of recovery as deeper formations are brought into production, has stimulated interest in methods for studying and predicting efficiencies of various production programs. Among methods Of recovery that have become of increased significance recently are gas recycling in condensate fields and secondary recovery by water-flooding. The electrolytic model is a useful device for studying such methods in the laboratory, at least in a qualitative way. The original experiments with electrolytic models and the development of their application to the study of secondary reCoverY problems were published in 1933. 1,2,3 Subsequently other investigators continued the development and modification of the bait method, with resultant improvements and extension of its applications.4-7 The method and equipment to be described here are thought to represent still further improvement in the results obtainable, with increased validity in their application to field problems. Sand OF Principles of Operation The underlying theory of the operation of the model is given in references I, 2 and 3. However, a brief statement of principles involved is given herewith. The applicability of the model is based on the fact that Ohm's law and d'Arcy's law are exactly analogous; whence, electrical flow through a conducting medium may be used to simulate homogeneous fluid flow through a permeable medium. If two electrodes are placed in a conducting (ionized) solution and connected to the positive and negative terminals of a source of direct current, the positive ions of the solution will move toward the negative terminal, Since the velocity of an ion in an electrolytic medium is proportional to the electrical gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the motion of the ions in the potential field will be the same as the motion of fluid particles in a porous medium if the positive and negative terminals (input and output wells) and boundary conditions are made equivalent in shape and distribution. In order for the analogy to hold exactly, the sand must be assumed to have uniform porosity and permeability and the input

Jan 1, 1946

Charles H. Morgan, Worcester, Mass. (communication to the Secretary): In connection with Mr. Douglas's mention of the continuous charcoal kiln used at Kopparberg, some further data concerning this important invention may be of interest. Before giving these, however, I will say a word or two concerning other features of Swedish practice. In 1894 I spent two days at Soderfers with Mr. Tom Bergendal, the manager of the works, and was specially interested in the gas-producers and wood-drying kiln, illustrated in the paper contributed to our Transactions by Mr. Odelstjerna in that year.* The wood-drying kiln is, however, quite different in design and construction from Ljungberg's charcoal kiln. In the summer of 1894 it was discovered that by placing the gas-producer as close as possible to the open-hearth furnace, and working the producer hot, ordinary weather-dried wood, still containing a considerable percentage of moisture, could be used to advantage in the melting-furnace. Hence, the dryingkiln was needed for wet wood only. One of the iron-works of the Udeholm Go. was the first to adopt the Lundin saw-dust gas-producer and condenser, enabling them to make gas from saw-dust containing 45 per cent. of moisture, and convey the gas from the condenser through wooden pipes to the Siemens steel-melting furnace.† This sawdust gas gave very satisfactory results in iron-works; but the proprietors experienced much trouble by reason of the pollution of rivers by the tar-water from the condenser. On my visit, in 1894,I found that the Udeholm Co. had put in for their steel-melting furnaces the same wood-gas producers

Jan 1, 1899

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,'-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;4'5'7 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'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'" 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 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 R. E. Reed, C. J. McHargue

Single crystals of aluminurn were reduced 90 pct in diameter by extrusion at 296" and 77°K. The resultant double fiber texture had a strong (111) component with a weak (001) component. The relative anzounts of these components varied with starting orientation. Decreasing the Lemperatuve of defovtnation increased the amount of (001) texture component in crystals with inilia1 orientations near (111). The starting orientation and temperature of deformation strongly affected the morphology of the (001) component. The effects of orientation and Lemperatuve upon the distribution of the (001 ) texture component in extruded aluminum single crystals were rationalized on the basis of deformation band formation and interaction. MANY papers since the early 1920s have discussed the occurrence of the double fiber texture (111) + (001) in wires and rods of deformed fcc metals. Aside from the reporting of experimental results for the various metals under a variety of fabrication conditions, emphasis has been placed on two related problems. One problem deals with the prediction of ideal end orientations based on the glide systems and flow directions. The other problem seeks the reason why different amounts of each component may be produced by the same fabrication schedule for metals apparently having the same deformation systems. Some of the difficulties in developing a satisfactory explanation have their origin in the experiments themselves. One mistake has often been the assumption of an initially randomly oriented specimen or complete ignorance of effects of starting orientation. Recent studies by Grewen and Wassermann,1 Cullity and co-workers,2' and McHargue4 have shown that the initial orientation may be the most important factor in determining the final orientation. Hence only limited comparisons of data from different studies can be made unless all conditions of the initial material are specified. Another question has been the nature of the (001) component. Hibbards suggested that any (001) present was the result of re crystallization during fabrication. Although Fleischer6 found no (001) texture in aluminum swaged at room temperature, and Dayal 7 found that component to disappear at very high reductions, a double fiber texture has usually been reported for aluminum. Vandermeer and McHargue showed that, while some (001) in aluminum may be the result of recrystallization, much of this component has its origin in the deformation process. Ahlborn and Wassermanng found the (001) component in silver deformed at low temperature not to be the product of recrystallization.

Jan 1, 1968

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By James P. Kimball

The object of the present memoir is to pot on record some practical experiments by the writer in smelting a silicions native magnetite with no other flux than the silicates of its own gangue.' This work was undertaken in the spring of 1878 for Messrs. Naylor & Co., of' Boston, to whom I am indebted for the privilege of here communicating its results, these having hitherto only been simply announced.* So far as I am aware these are the first instances of the kind ill this country that non-calcareous; or rather non-carbonatbed, magnetite have successfully been used strictly alone as self-fluxing ores in the blast furnace; that is, without the addition of' calcareous flux in the form either of limestone, quicklime, calcareous ore, or basic (calcareous) slag. Previous to the spring of 1878, when the Chateaugay magnetic ore was first brought to illy notice. its use had been limited to Catalan forges, after " separation " at the ore bed. The blooms and billets made from it in the several forges of Messrs. Weed $ Williams, and of Mr. Williams, were well known in the trade as among the best in the market. Tile Chateaugay ore beds proving of great magnitude, and the ore exceptionally low in phosphoric acid, it commended itself for blast-furnace purposes to Messrs. Naylor & Co., who employed me to blow-in the charcoal furnace at Pittsford, Vt., on this ore in the spring of 1878, a previous trial of this ore in the same furnace in the fall of 1877 having proved abortive. This was therefore the first time that Chateaugay ore was successfully smelted in a blast furnace, although since well known as a blast-furnace ore possessing superior and exceptional qualities. The Pittsford furnace, although rebuilt in 1844, and subsequently improved by the former owner, the late J. Prichard, is one of the few furnaces of the old type with open breast (Sumpfofen) still active in this country, Its improvements 011 furnaces of the period,

Jan 1, 1881

By Leonard Larson

Before direct or wet smelting of copper concentrate was adopted at the McGill smelter, in November 1932, actual furnace smelting tests had indicated the possibility of smelting between 400 and 500 dry tons of wet concentrate per furnace day. Under calcine smelting practice, solid charge up to 116; tons per furnace day had been smelted. It was realized that in order to smelt wet tonnage in equivalent amount per furnace day, a higher combustion rate and higher temperatures would be necessary within the furnace. The reverberatory furnace considered in the following history of wet-smelting developments is a unit rz7 ft. long and 28 ft. 8 in. wide, inside dimensions (Fig. I). This furnace was in operation through all the years from 1934 to date. During 1933, the first complete year of direct or wet smelting, the plant was on a curtailed copper-production basis and the available concentrate tonnage to be smelted was limited. The average coal-firing rate in the reverberatory for that year was 124 tons per furnace day. This rate was lower than the average for years immediately preceding under calcine smelting practice. With this coal-firing rate, an average of 391 tons of new metal-bearing material (N.M.B.M.) was smelted per furnace day. The following year, 1934, the coal-firing rate was increased to 139 tons and the smelting rate increased to 448 tons N.M.B.M. per fur- nace day. In succeeding years production required that either more tonnage be smelted in the one furnace or an additional furnace be placed in operation. With this situation confronting the smelting department, it was determined to continue the program of increasing the coal-firing rate and also to intensify the temperature in the smelting zone of the furnace. In order to accoinplish this, various improvements were made to aid combustion within the furnace. The burners were enlarged, increased primary air was supplied to the burners, and changes were made in the furnace to enlarge and streamline the outlet, thus increasing the furnace draft. The coal-firing rate was increased yearly until 1937 when the firing rate averaged 210 tons per furnace day. Thereafter the firing rate fluctuated according to character of charge and production requirements. In general, however, with the same character of charge the smelting rate increased in almost direct proportion to the increases in firing rate. Table I shows the average coal-firing rate, smelting rate, and other pertinent data for the direct-smelting years of 1933 to 1939 inclusive, the first fivc months of 1940 and May 1940. These figures show that the water evaporated in the waste-heat boilers was in almost direct proportion to the coal-firing rate. In making comparisons in the table, it should be borne in mind that the figures, except for May 1940, are yearly averages. Because of changes in character of charge or operating conditions, records for individual days or even months

Jan 1, 1944

By Joseph Chalmers, J. S. Desmond, R. Van A. Mills

[Because of the limited space in this volume and the fact that a description covering the oil recovery buildings and equipment (see page 4, Technical Publication No. 144) will be given in a forthcomnig U. S. Bureau of Mines publication, and because the paper was published in detail as Technical Publication No. 144, and is available as a separate at the Institute, it is impossible to include here more than the following brief extract.] Problems Being Studied The selection of the first problems to be studied was based largely upon the following very practical questions asked by several of the largest operators in the Mid-Continent field. 1. What are the causes for the formation of excessive amounts of bad thick oil on properties that are being repressured with compressed air and how can this trouble be prevented? 2. Why, in some areas, does the oxygen in the air injected into an oil sand during repressuring operations apparently change to carbon dioxide? Is carbon dioxide formed by the oxidation of some of the oil in the sand'? How can the formation of inert or low B.t.u. casinghead gas, loaded with nitrogen, carbon dioxide and oxygen, be prevented? 3. What percentage of the oil originally present in an oil sand can be recovered by the ordinary methods of operation when the gas originally dissolved in the oil is the main propulsive agent? 4. What percentage of the amount of oil produced by ordinary methods can be recovered under average conditions by repressuring a so-called depleted oil sand? 5. What are the relative propulsive efficiencies of compressed air and natural gas in repressuring operations? 6. What are the practical advantages of pressure maintenance and early repressuring as compared with late repressuring?

Jan 1, 1929

By A. Rosen, P. Wynblatt, J. E. Dorn

The temperature, strain rate, and structure dependence of the flow stress in a poly crystalline Fe-2 pct Mn alloy was investigated between 77" and 370°K. It was possible to identify the low-temperature data from 77° to 160°K with Dorn and Rajnak's theory of the Peierls mechanism of plastic deformation. Above 160°K one or more thermally activated mechanisms must he operative; however, these were not identified in this investigation. The mechanistic basis for the rapid decrease in the flow stress of bcc metals with an increase in temperature over the low-temperature range is yet being debated. Various dislocation mechanisms have been suggested in the past but the agreement between the various proposed theories and the experimental results have not been definitive. In the present paper, the authors will demonstrate that the plastic behavior of polycrystalline iron containing 2 wt pct Mn plus interstitials agrees excellently with predictions based on the Peierls mechanism from 77" to 160°K whereas from 160" to about 370°K other as yet unidentified thermally activated mechanisms take over. Undoubtedly, the overlap of these mechanisms with the Peierls mechanism contributed to the difficulties of rationalizing the low-temperature behavior of iron and its alloys. I) EXPERIMENTAL TECHNIQUES AND RESULTS Although extensive data are now available on the effect of temperature and strain rate on the flow stress of various bcc metals and alloys, it was, nevertheless, deemed necessary for the objectives of the present study to obtain highly accurate data of the type most pertinent for checking the theories on a series of well-documented work-hardened states. Iron containing 2 wt pct Mn was used in this investigation in order to obtain a lower ductile to brittle transition temperature than that for iron.' The additional elements present were 0.004 pct C, 0.05 pct 0, 0.004 pct S, 0.003 pct P, 0.006 pct N, and 0.001 pct Si. The as-received 3/8 by 3/4 in. bars were cold-rolled to 0.100-in. thickness, recrystallized under argon for 30 min at 1073"~, further cold-rolled to 0.063-in. thickness, and finally recrystallized under argon for 30 min at 1000°K. This treatment gave a stable reproducible equiaxed grain structure having an average grain diameter of about 90 p. Prior to the final recrystallization treatment, the sheet was machined into tensile specimens 1/4 in. wide having a 1.625-in.-long gage section. All specimens were tested in controlled-temperature baths on an Instron Testing Machine. For convenience in the theoretical analyses the data will be given in terms of the shear stress for flow, 7, the shear strain rate, f, and the shear strain, y. A series of three standard strain-hardened states were obtained by prestraining specimens at 300°K and at a shear strain rate of 7.68 x lo-' per sec to three stress levels of 6.89 X l08, 10.3 X lo8, and 14.5 x 10' dynes per sq cm, respectively. Immediately following this prestrain the temperature bath was changed and each specimen was pulled in tension at either f = 7.68 X lo-' or f = 3.06 X 10"3 per sec. In terms of the accuracy that was achieved, the values obtained did not deviate more than *0.1 X 10' dynes per sq cm and * 1°K from the reported values of stress and temperature and not more than *5 pct in the reported values of the strain rate. The tensile stresses were converted to shear stresses using a factor of 1/2. The shear stress for the initiation of flow at the test temperature was determined by taking a y = 6.16 x 10'3 offset. from the modulus line at which point good accuracy could be achieved in determining y and the associated flow stress 7, with only a negligible increase in the pre-

Jan 1, 1965

By J. P. Sheeha, W. F. Craig, M. Baeyertz

The loss in toughness caused by phosphorus within commercial ranges was studied in AISI-SAE 1340 steel and in molybdenum modifications of this grade. The replacement of part of the manganese by molybdenum in amounts which maintain the hardenability of the standard 1340 grade was shown to counteract to a marked degree the detrimental effects of phosphorus. THIS paper deals with the effect of phosphorus on the toughness of 1340 steel and with the effect on toughness of replacing part of the manganese by molybdenum while retaining the same hardenability as that of 1340. In previous work1 a progressive decrease in toughness was observed when the phosphorus content of 5140 was raised from 0.020 to 0.036 pct; that is, from a moderate phosphorus level to one higher but yet within the AISI-SAE specification for this grade. The structural condition of the steel was tempered martensite. Toughness was evaluated by the transition temperature determined by V-notch Charpy tests. Replacement of a part of the chromium in 5140 by molybdenum provided a factor of safety against loss of toughness caused by phosphorus, especially where the steel was cooled slowly after tempering. Scope of the Study: In view of the improved tolerance for phosphorus obtained by replacing a part of the chromium in 5140 with molybdenum, it seemed desirable to investigate the possibility of obtaining similar improvement in 1340 by replacing part of the manganese with molybdenum. Heats were made at different phosphorus levels, in a series that began with 1340 and ended with steels containing 0.32 to 0.35 pct Mo with 0.82 and 0.90 pct Mn. The analyses of the heats are given in table I. In order to facilitate later discussion, the 1340 heats have been placed together in the order of increasing phosphorus content, and the molybdenum modifications have been grouped according to phosphorus

Jan 1, 1951

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By Norman Brown, J. V. Rinnovatore

It was found that a shear stress applied during the recovery had no effect on the amount of recovery if the stress was less than the instantaneous yield point irrespective of the direction of the stress. Large ajplied stresses during recovery had a marked effect, which depended on the direction of stressing. Single strain reversals at -72°C not only produced the Bausch-inger effect but also increased the flow stress. The increase inflow stress was attributed to vacancies, which have appreciable mobility at -72 °C. THEORIES I-' of recovery suggest that the internal stress field of the dislocations plays an essential role. Most investigations of recovery use time and temperature as the independent variables; however, here stress has been introduced as a variable in two ways: 1) by varying the internal stress field according to the amount of strain prior to recovery and 2) by applying an external stress during recovery. Tannen- baum and Kauzrnann studied the effect of applying a stress during recovery by measuring the change in creep rate after recovery; they found that stresses as high as 95 pct of the creep stress had no effect on recovery. Earlier, Wood and scrutton6 showed that an applied stress during creep increased the rate of poly-gonization. The experiment by Wood involved poly-crystalline aluminum whereas Tannenbaum and Kauzmann used a single crystal of zinc. In this investigation, zinc single crystals were used and deformed in a manner to prevent polygonization. Thus, the main difference between this investigation and that of Tannenbaum and Kauzmann is the use of the stress-strain curve instead of creep rate as the index of recovery. In addition, the applied stress during recovery varied

Jan 1, 1961

By Robert D. Pehlke, Kazuhisa Okajima

The activity of zinc in dilute liquid lead alloys containing small additions of silver and gold has been measured using a multielectrode galvanic cell with a fused chloride salt electrolyte. The range of temperatures studied in the Pb-Zn-Ag system was 550" to 670°C and in the Pb-Zn-Au system was 680" to 800°C. The interaction parameters between zinc and the precious metals in the respective temperature ranges are ThE lead-rich corners of the Pb-Zn-Ag and Pb-Zn-Au ternary systems are of considerable industrial importance. The use of zinc additions for the desilvering The results of this investigation have Provided a senzi-quantitative determination of the liquidus phase boundaries in the lead-rich corner of these ternary diagrams. of liquid lead either by the Parkes process or by the more recent Williams continuous process is an important refining phase of lead production.1 Several in-ve~ti~ations~-~ have been carried out on the Pb-Zn-Ag system with the hope of improving the efficiency of refining lead in this manner. The addition of zinc also provides a means for separating gold from lead. Since gold is eliminated more easily than silver, a two-stage removal of gold and silver is possible.8'7 The thermodynamic interactions between zinc and these precious metals in dilute solution in liquid lead

Jan 1, 1968