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By H. W. Russell, H Pray, Paul D. MILLER

It is known that austenitic chromium-nickel steels that have free carbide in the grain boundaries are subject to intergranu-lar corrosion. It is difficult to detect such a susceptible condition in a fabricated article because present test methods require a sample section for examination and in most cases this is difficult to obtain. The question of the nature and prevention of intergranular corrosion in austenitic stainless steels has been ably discussed by Bain and co-workers1-3 and by other investigator4-10 The present methods of study subject samples to corrosive conditions in such reagents as the Strauss solution, a mixture of copper sulphate and sulphuric acid. Such tests usually require at least 72 hr. to run. Various methods of measuring the degree of sensitization have been employed, such as the measurement of electrical resistivity, magnetic measuremerits, measurement of the degree of cracking produced on bending over a malldrel, and microscopic studies. The detection of carbides at the grain boundaries by metallographic polishing and etching methods is tedious and requires a skilled operator. A recent report on such methods of carbide detection is given by the American Society for Testing Materials Subcommittee VI of Committee A.-1011 and by Arness.12 The present investigation was undertaken to develop a simple test procedure for detecting carbide precipitation or susceptibility to intergranular corrosion. The test is designed for use in the plant and for the testing of fabricated structures. Carbide precipitation, the factor leading to susceptibility to corrosion, is produced by heating the alloy in the temperature range 800° to 1600°F., as in welding, in improper annealing or in service where such temperatures are met. The connection between such precipitation and susceptibility to corrosion has been thoroughly discussed, as has been the use of stabilizing addition elements to prevent precipitation. Experimental Method A small area of the steel under test is subjected to an anodic treatment in a cell that can be 'lamped Onto a a Or an actual structure. The cell and electrical circuit used are illustrated in Fig. I. The cell C is lead, joined to the steel plate D and insulated from it by a short piece of rubber tubing E. The cell is forced tightly against the steel plate by a spring Or clamping device. The seal formed by the rubber against the steel plate is sufficient to retain the liquid bath inside the cell. The spot treated can be made any shape desired, depending on the shape of the rubber gasket. The cell illustrated polishes a circular spot about 3/8- diameter' The bath consists of 60 per cent (by weight) sulphuric acid to which is added 5 ml. per liter of Glycyrrhiza extract (U.S.P.). The cell requires about 2 to 2.5

Jan 1, 1941

By John Chipman, Eric R. Jette, O. B. Ellis

IN the study of the chemical reactions occurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Herty1 and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schackmann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete analyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were remelted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abandoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the constituents of basic open-hearth slag. EXPERIMENTAL HEATS The first set of measurements on slagmetal equilibrium was made in the Research Laboratories of the American Rolling Mill Co. at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Research Laboratories at Massachusetts Institute of Technology, and will be referred to as series B. Series A.-The induction furnace used has been described.5 Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

AS I have told you before, "alloy" here signifies nothing but the mixture of one metal with another in friendly companionship. Whenever you wish to do this, you should consider the purpose that moves you, whether it is to increase the quantities, or for corruption. Then you should choose whatever has by its nature more affinity with what you wish to alloy, or whatever is best for your purpose. Give it in the melt the proportion that you wish or as much as it can support without being entirely removed from its first nature, as [73v] water is in wine or white in black if too much is added. However, you must make the proportion with a definite ratio by weight and not by chance in order that you may bring your work to the degree of perfection that you desire. For he who, proceeds with his eyes closed not only stumbles many times but frequently falls. Therefore you must know first that gold does not join in an alloy with any metal other than silver and copper. Thus if you wish to make a work of gold or to have it made, and begrudge the expense of having it fine, or if you find that you do not have enough, or if you do not care about such fineness, you must decide exactly how many carats less than perfectly fine you wish it to be, or by what weight you wish it to be increased. In order to do this accurately weigh the fine gold that you have and accompany it with silver or fine copper in the quantity that you wish to give it, and melt both these things together very well. So that you may understand the procedure better, let us suppose that you wish your gold to be 23 carats. You are to imagine that the whole quantity is twenty-four parts because this is the final limit at which the gold can be perfect. Now if this were the case, you would put in one part, which corresponds to one twenty-fourth of the whole quantity. You will have taken away one carat of the value of its fineness and increased it another in quantity. In the same way it will happen if you put in two or three or four or six. Up to the limit of one-half, you will always have gold according to the denomination of the lesser virtue and the greater quantity. Surpassing one-half, so that there are eleven parts of silver and thir-

Jan 1, 1942

By Jim Douglas, H. H. Rachford, D. W. Peaceman

The problem of unsteady-state gas flow through porous media has been solved numerically only for the case of linear or radially symmetric reservoirs. A recently introduced numerical method for solving the unsteady-state heat flow equation in two dimensions is applied to the calculation of the depletion of a square region containing a perfect gas. Solutions are presented in graphical form for various values of dimensionless parameters. The solutions are compared with published .solutions for radial reservoirs. I NTR ODUCTION The problem of unsteady-state flow of gas through porous media gives rise to a second-order non-linear partial differential equation for which no analytical solution has been found. Numerical approximations to solutions of the gas flow problem have been obtained by the stepwise solution of an associated difference equation1,2. However, the methods so far developed have required that the reservoir be either linear or radially symmetric. This restriction in shape has been necessary so that only two independent variables be considered, namely, one distance variable and time. In order to deal with reservoirs having more realistic shapes, it is necessary to develop numerical procedures for the solution of the gas flow problem involving two distance variables. A numerical procedure, denoted as the alternating-direction implicit method, for the solution of the heat-flow problem in two dimensions has recently been introduced" By the use of this procedure, approximate solutions have been obtained for heat-flow problems in a square8, and in regions having various non-rectangular boundariesa. Because of the similarity between the equation for heat conduction in solids and the equation for gas flow in porous media, it is reasonable to expect that the alternating-direction implicit method should also be useful for solving the gas flow problem in various two-dimensional regions. Solutions have been calculated for the simplest two-dimensional region, a square reservoir with a single well in the center. While reservoirs of such simple geometry seldom, if ever, exist, the solution of this problem is of some practical importance because it is also the solution of another problem, that of determining the depletion history about an individual well in an infinite uniform reservoir containing wells spaced throughout on a square lattice and producing equally from each well. Finally, it is of interest to compare solutions for a square reservoir with those for a circular reservoir and to determine the effect of the shape of the boundary for that particular case. METHOD OF CALCULATION Basic Differential Equation By combining the equation of continuity, the perfect gas law,

Jan 1, 1956

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y' precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y' might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,' were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.'" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By W. F. Dietrich

Mineral fillers are relatively inert chemically under the conditions of use but have physical properties* that modify those of the materials • The properties. uses, and other data on 15 classes of important *The pro listed in the second edition of Industrial Minerals and Rocks.l A third edition of this reference is in preparation. in which they are incorporated. The mineral fillers considered in this article are asbestos, barite, clays, diatomite, crushed limestone, limestone whiting and lime, mica, silica, talc and soapstone, and pyrophyllite. Slate and stone, other than limestone and its derivatives, are excluded because, even though used in large quantities, they are exceptionally low-cost materials generally produced close to the area where they are used. Carbon black is excluded because it is manufactured from natural gas and more than 90 pct of the output is used in rubber; hence the factors for estimating requirements are easily evaluated. OVERALL GROWTH FACTORS Table I gives the population, retail sales, and value added by manufactures in the U. S. and in the eleven western states in 1954. These data are rough guides to the proportionate part of total U. S. markets for products containing mineral fillers that may be expected in a given area. For example, the population of the eight Mountain states in 1954 was 3.6 pct, and retail sales in these states were 3.8 pct of the U. S. total, but the value added by manufactures was only 1.3 pct of the U. S. total. On the other hand, the three Pacific Coast states, with 10.3 pct of the total population, had 12.0 pct of the retail sales and produced 9.6 pct of the value added by manufactures. On an industry-by-industry basis the correlation between the three guideposts will not be as close as shown in the 1954 data for the Pacific Coast states, but in the long-term view the continuing rapid population growth in the western states is certain to result in expanded industrial production at an even more accelerated pace, which will shorten the gap between local consumption and production in most major groups of manufactured consumer goods. Of course, there will always remain favorable areas for production of specific products. Such special situations must be individually analyzed. Fig. 1 compares the population trends in the U. S., the western states, and California with Real Gross National Product from 1910 to 1957, with forecasts to 1970. It is estimated' that the U. S. Real Gross National Product, as measured by the value of goods and

Jan 1, 1960

By O. B. Ellis, Eric R. Jette, John Chipman

In the study of the chemical reactions orcurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Hertyl and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schack-mann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete allalyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were re-melted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abnndoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the con stituents of basic open-hearth slag. Experimental Heats The first set of measurements on slag-metal equilibrium was made in the Research Laboratories of the American Rolling Mill Co, at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Rescarch Laboratories at Massachusetts Institute of Techology, and will be referred to as series B. Series A.—The induction furnace used has been described. Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

By John Chipman, Eric R. Jette, O. B. Ellis

In the study of the chemical reactions orcurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Hertyl and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schack-mann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete allalyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were re-melted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abnndoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the con stituents of basic open-hearth slag. Experimental Heats The first set of measurements on slag-metal equilibrium was made in the Research Laboratories of the American Rolling Mill Co, at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Rescarch Laboratories at Massachusetts Institute of Techology, and will be referred to as series B. Series A.—The induction furnace used has been described. Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

By W. T. Lankford, Edward Saibel

During the course of an investigation of the plastic flow of aluminum aircraft sheet under combined loads, several problems arose in which analyses of the conditions leading to unstable plastic flow were needed. In order to provide these analyses, and in the hope of attaining a better understanding of the general problem of unstable plastic flow, the present study was undertaken. It is well known that unstable plastic flow is associated with a form of mechanical instabi!ity frequently observed during the plastic deformation of ductile metals. This instability is characterized by the fact that, at its onset, plastic straining mill proceed at a constant magnitude of the externally applied forces. It is further typical that the resulting unstable flow is generally accompanied by the formation of a neck, a local bulging, or some other form of heterogcneous deformation. Perhaps the most familiar example of unstable plastic flow to the metallurgist is the formation of the neck in the ordinary tension test. It is well known that in this test most metals exhibit a maximum in the externally applied load, followed by the process commonly referred to as "necking down." Instability in the simple tension test has been frequently discussed and numerous investigators1'2'3'12 have derived the criterion for instability in terms of a critical rate of strain hardening. It is the purpose of the present study to extend the criterion for unstable flow to the more general case where the body undergoing flow is subjected to combined loads. It is hoped that the problems considered will provide a more consistent picture of the general features of this important form of mechanical instability. The most practical implications of instability in plastic flow arise in connection with sheet metal forming operations. In the formation of a great many sheet metal parts, the deformations are produced primarily by stretching. If the conditions which lead to unstable flow are fulfilled in such a formation, and if the resultant instability leads to a pronounced localization of flow, then the useful limit of ductility of the material will have been reached. It i; also essential that the effects of instability be taken into consideration in any study of the plastic flow and rupture of metals under combined stresses. In general, when unstable plastic flow is initiated, straining becomes localized, the geometry of the test splecimen changes, and the state of stress in that portion of the specimen undergoing plastic flow is no longer under external control. In many past studies of the effects of combinetl Metals On flow and rupture) account has not been taken of the fact that, although a given test may be started under constant

Jan 1, 1947

By Edward Saibel, W. T. Lankford

During the course of an investigation of the plastic flow of aluminum aircraft sheet under combined loads, several problems arose in which analyses of the conditions leading to unstable plastic flow were needed. In order to provide these analyses, and in the hope of attaining a better understanding of the general problem of unstable plastic flow, the present study was undertaken. It is well known that unstable plastic flow is associated with a form of mechanical instabi!ity frequently observed during the plastic deformation of ductile metals. This instability is characterized by the fact that, at its onset, plastic straining mill proceed at a constant magnitude of the externally applied forces. It is further typical that the resulting unstable flow is generally accompanied by the formation of a neck, a local bulging, or some other form of heterogcneous deformation. Perhaps the most familiar example of unstable plastic flow to the metallurgist is the formation of the neck in the ordinary tension test. It is well known that in this test most metals exhibit a maximum in the externally applied load, followed by the process commonly referred to as "necking down." Instability in the simple tension test has been frequently discussed and numerous investigators1'2'3'12 have derived the criterion for instability in terms of a critical rate of strain hardening. It is the purpose of the present study to extend the criterion for unstable flow to the more general case where the body undergoing flow is subjected to combined loads. It is hoped that the problems considered will provide a more consistent picture of the general features of this important form of mechanical instability. The most practical implications of instability in plastic flow arise in connection with sheet metal forming operations. In the formation of a great many sheet metal parts, the deformations are produced primarily by stretching. If the conditions which lead to unstable flow are fulfilled in such a formation, and if the resultant instability leads to a pronounced localization of flow, then the useful limit of ductility of the material will have been reached. It i; also essential that the effects of instability be taken into consideration in any study of the plastic flow and rupture of metals under combined stresses. In general, when unstable plastic flow is initiated, straining becomes localized, the geometry of the test splecimen changes, and the state of stress in that portion of the specimen undergoing plastic flow is no longer under external control. In many past studies of the effects of combinetl Metals On flow and rupture) account has not been taken of the fact that, although a given test may be started under constant

Jan 1, 1947

By W. E. Horst

John Dasher (Central Research Laboratory, Crucible Steel Co. of America, Pittsburgh. Pa.)— Getting spodumene to float quickly and cleanly can be a problem. The author has presented an excellent account of a valid and useful approach to the scale-up of such problem floats. This indicated advantages for doubling retention time, i.e., buying another set of flotation cells. The author states that 21 pct of the spodumene floated in 2 min in the laboratory cell, that the grade of the rougher was about 75 pct spodumene, and that the final tailing contained 4 to 12 pct spodumene in different sizes with the present cells and 1 to 9 pct spodumene with twice as many cells. About 20 years ago, this writer obtained in the laboratory the flotation of over 90 pct of this spodumene in a King's Mountain sample in 1 min at a grade of 90 pct spodumene in the rougher and a final tailing that contained only 1 pct spodumene. The methods of Norman, Ralston," and Gieseke' were used, which teach that spodumene floats quickly and cleanly if its surfaces have been properly conditioned chemically and/or mechanically prior to flotation. Although feed preparation is not discussed, the results reported indicate that it is inadequate. This writer suggests that improvements in this area might be more effective than doubling the number of cells. W. E. Horst (author's reply)—Dasher's comments are appreciated by the author and require some clarification. He suggests that improved spodumene flotation performance may be obtained by feed preparation techniques rather than increased retention time in flotation. Certainly flotation performance is dependent on feed preparation and this is an important feature in the flotation process. It is true that certain types of spodumene ores, particularly weathered ores, require more complicated feed preparation processing than clean ores to achieve the desired flotation results. It was not implied that current feed preparation techniques are the same as experienced during the scale-up investigations. Although discussion of feed preparation was omitted from the article on scale-up relationships, the important feature was that pre-treatment processing was the same for each level of operation investigated— laboratory, pilot plant, and plant scale. Under these similar conditions large differences existed in recovery for comparable time intervals in each scale of operation. It is highly probable that feed preparation techniques could be modified and thereby increase the flotation rate for each scale or all scales of operation discussed. However, modifications would have to be justified on an economic basis.

Jan 1, 1960

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By C. S. Lyons and. A. L. Johnson

A few years ago a leading American builder of centrifuges said, "No one uses a centrifuge if the job can be done any other way." This statement was essentially true at that time, not because the basic functional and economic principles involved did not frequently favor centrifugal methods, but rather because so many of the highly specialized features of the mechanical and functional peculiarities of continuous centrifuges had not been fully developed. The idea of using centrifuges in mineral dressing is definitely not new. There are literally hundreds of patents on centrifugal machines and processes for the mining industry. Many of them cover principles that are basic to the functioning of most centrifuges in operation today. In spite of this, until 1935, there were practically no successful applications of continuous centrifuges in the United States in the mineral industry, nor for that matter were there more than a mere handful of such machines in operation in North America in any industry. This was true despite the obvious desirability of machines that could furnish the advantages of high centrifugal settling forces in a continuous operation. The reasons for this are simple, even if not obvious: I. Finely divided solids, when thrown out of fluid suspension under high cen- trifugal forces, frequently exhibit physic a properties (particularly rheological or flow properties) that are markedly different from those they possess when settled out by gravity alone, and machines that are not designed in careful detail to cope with these peculiarities 'seldom function satisfactorily. 2. Most continuous centrifuges embody a solids-conveying element in the form of a very special screw conveyor. The rotation of this member under conditions of operation culls for drive designs that were not satisfactorily provided until the introduction of the Bird gear unit about 1934. These matters will be touched on later. Continuous centrifuges are now operating successfully in the mineral industry. Some units have singly handled more than 500,000 tons of solids during the past ten years. Generally their operation has been characterized by large unit capacities, complete elimination of labor, minimum supervision, moderate maintenance and power costs. Typical Centrifuge Applications Most materials classified by centrifuges are of subsieve particle size. Practically speaking, this means her than 100-mesh. A unit of measure other than screens is needed in order to consider these products properly. Such a unit is the micron, which is equal to one one-millionth of a meter; roughly1/25,000 of an inch. The opening in a standard 200-mesh screen is about 75 microns while a 325-mesh opening is roughly 43 microns.

Jan 1, 1948

By C. S. Lyons and. A. L. Johnson

A few years ago a leading American builder of centrifuges said, "No one uses a centrifuge if the job can be done any other way." This statement was essentially true at that time, not because the basic functional and economic principles involved did not frequently favor centrifugal methods, but rather because so many of the highly specialized features of the mechanical and functional peculiarities of continuous centrifuges had not been fully developed. The idea of using centrifuges in mineral dressing is definitely not new. There are literally hundreds of patents on centrifugal machines and processes for the mining industry. Many of them cover principles that are basic to the functioning of most centrifuges in operation today. In spite of this, until 1935, there were practically no successful applications of continuous centrifuges in the United States in the mineral industry, nor for that matter were there more than a mere handful of such machines in operation in North America in any industry. This was true despite the obvious desirability of machines that could furnish the advantages of high centrifugal settling forces in a continuous operation. The reasons for this are simple, even if not obvious: I. Finely divided solids, when thrown out of fluid suspension under high cen- trifugal forces, frequently exhibit physic a properties (particularly rheological or flow properties) that are markedly different from those they possess when settled out by gravity alone, and machines that are not designed in careful detail to cope with these peculiarities 'seldom function satisfactorily. 2. Most continuous centrifuges embody a solids-conveying element in the form of a very special screw conveyor. The rotation of this member under conditions of operation culls for drive designs that were not satisfactorily provided until the introduction of the Bird gear unit about 1934. These matters will be touched on later. Continuous centrifuges are now operating successfully in the mineral industry. Some units have singly handled more than 500,000 tons of solids during the past ten years. Generally their operation has been characterized by large unit capacities, complete elimination of labor, minimum supervision, moderate maintenance and power costs. Typical Centrifuge Applications Most materials classified by centrifuges are of subsieve particle size. Practically speaking, this means her than 100-mesh. A unit of measure other than screens is needed in order to consider these products properly. Such a unit is the micron, which is equal to one one-millionth of a meter; roughly1/25,000 of an inch. The opening in a standard 200-mesh screen is about 75 microns while a 325-mesh opening is roughly 43 microns.

Jan 1, 1948

By John M. Hartman

(Read at the Wilkes-Barre Meeting, May, 1877.) Two systems are used for heating air in blast-furnace operations I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100° F. as a maximum temperature of the blast. II. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more complex than the double surface, as it involves the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300° F. to 1400° F. is the best average temperature for economy of coal for safe work¬ing. This is equivalent to a saving of 12 to 2 cwt. of coal per ton, of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the value of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxy¬gen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800° in place of 1100°, it is obvious that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calories lost to the hearth must be regained before good iron can be made. Take another case : A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1878

By Harvey S. Mudd

AMONG the highly skilled craftsmen of the Renaissance were those who worked with ores and metals. The author of this book, Vannoccio Biringuccio, was a master craftsman in the practices of smelting and of metalworking. Contrary to the customs of a trade, Biringuccio was moved to impart his knowledge to all and thus he has given us the earliest hand- book on metallurgy-in fact, the first printed book dealing with the applied metal arts and the processes of ore reduction. We should remind ourselves that metallurgy is an ancient art and then it fair1y may be said that Biringuccio sought to describe the techniques that had been in course of development since the Bronze Age of western civilization. Whether Biringuccio was a man of learning or a scholar according to the standards of his time we do not know, but today we recognize him as a man of science who gave his wisdom to succeeding generations. It was not until the coming of the Power Age at the end of the eighteenth century that progress was resumed in the science of which he wrote more than two hundred years before. Little is known of Biringuccio's training in his native Siena. It can be surmised that there, as in Florence, where his contemporary Benvenuto Cellini lived, he received his training in the craftsman shops where the industrial arts were taught and flourished alongside the fine arts. Perhaps he and Cellini were acquainted, although there is no mention of Biringuccio in Cellini's autobiography-an omission that Cellini's vast egotism makes understandable. He was the great artist, and Biringuccio was a practical, studious, unromantic figure with no favors to dispense. In the April 1940 issue of Mining and Metallurgy Dr. Smith describes Biringuccio's book under the title of "A Neglected Italian Metallurgical Classic." The article, revised and extended, forms the basis of the introduction to the present volume, and I urge all who take up Pirotechnia to read what Dr. Smith has written in the Introduction. Biringuccio's work is a classic and in its translation Dr. Smith and Dr. Gnudi have brought to bear the high degree of scholarship that it deserves. Dr. Gnudi made the translation at Dr. Smith's request and it was then refined "in the fire" of his scientific knowledge of the subject. The result is a book which the Institute is proud to place before its members and which the Memorial Fund Committee considers it a privilege to publish.

Jan 1, 1942

By John M. Hartman

TWO systems are used for heating air in blast-furnace operations: I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100" F. as a maximum temperature of the blast. 11. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more comylex than the double surface, as it invoives the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300" F. to 1400' F. is the best average temperature for economy of coal for safe working. This is equivalent to a saving of 11/2 to 2 cwt. of coal per ton of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the ralue of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxygen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800" in place of 1100°, it is obvions that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calorics lost to the hearth must be regained before good iron can be made. Take another case: A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1879

By R. T. Hukki

John F. Myers (Consulting Engineer, Greenwich, Corm.)—Since the art of comminution has lain practically dormant for many years, it is very interesting that R. T. Hukki approaches the subject with a new concept. One is reminded of the research carried on by A. W. Fahrenwald of Moscow, Idaho, a few years ago. Fahrenwald mounted a steel bowl on a vertical shaft. The balls and ore placed in the bowl were rotated at fast speeds, thus simulating the supercritical speeds used by Hukki. The rolling action of the balls against the smooth shell liner has pretty much the same effect. The action is horizontal in one case and vertical in the other. Both researchers report good grinding activity. It is also constructive that such able investigators give to the students of comminution their interpretation of their laboratory results in terms of large-scale operation. History shows that it takes a lot of time for such radically new ideas to be absorbed by the industry. Typical of this is the present-day activity of cyclone classification in primary grinding circuits. The idea of cyclone classification has been kicking around for 30 or 40 years. Certainly we all suspect that the ponderous grinding mills of today, and their accessory apparatus, large buildings, etc., will ultimately give way to small fast units, just as this has occurred in other industries over the past 50 years. At the moment there is no evidence that ball and liner wear is prohibitively high. In fact, at the time Fahrenwald was demonstrating his high-speed horizontal machine at the meeting of the American Mining Congress, several years ago, he assured this writer that the balls retained their shape much longer than they do in conventional tumbling mills. Rods and balls that slide (as some operators in uranium plants are experiencing) get flat. Apparently the balls have a rolling action. Mr. Hukki's references to the processing capacity of the Tennessee Copper Co. mills is adequate. Those studying this subject will be greatly interested in the paper presented by Richard Smith of the Cleveland-Cliffs Iron Co. at the annual meeting of the Canadian Institute of Mining and Metallurgy in Vancouver April 24, 1958. This paper will be published during the latter part of 1958 in the Canadian Institute of Mining and Metallurgy Bulletin. Hukki's pioneering spirit is to be commended. R. T. Hukki (author's reply)—It has been heartening to read the objective discussion by J. F. Myers. The sincerity of his opinions is further strengthened by the fact that the article he has discussed contradicts in a major way the parallel achievements of his life work. Myers is right in his opinion that in general it takes a long time before new ideas are accepted by the industry. On the other hand, revolutions usually take place at supercritical speeds. There are many indications at present that both the unit operation of grinding and the related subject of size control are now just about ripe for a revolution. In grinding, brute force must ultimately give way to science. Rapid progress can be anticipated in the following fields: 1) Autogenous fine grinding at supercritical speeds will be the first advance and the one that will gain recognition most easily on industrial scale. At this moment, little Finland appears to be leading the world. Crocker recently made a statement that in nine cases out of ten, your own ore can be used as grinding medium more effectively and far more economically than steel balls. This is true. The present author would like to introduce a supplementary idea: In eight cases out of the nine cited above, it can be done at the highest overall efficiency in the supercritical speed range. Fine grinding must be based on attrition, not impact. The path of attrition may be vertical, horizontal, even inclined. 2) In coarse grinding, the conventional use of rods is sound practice. However, even the rods can be replaced by autogenous chunks large enough to offer the same impact momentum as the rods. To obtain the momentum, the chunks must be provided with a free fall through a sufficient height in horizontal mills operated at supercritical speeds. Coarse grinding must be based on impact. Detailed analysis of the subject may be found in a paper entitled "All-autogenous Grinding at Supercritical Speeds" in Mine and Quarry Engineering, July 1958. 3) All conventional methods of classification, including wet and dry cyclones, are inefficient in sharpness of separation. Continuous return of huge tonnages of finished material to the grinding unit with the circulating load is senseless practice. In the near future the present methods will be either replaced or supplemented by precision sizing. These three fields are also the ones to which J. F. Myers has so admirably contributed in the past. Fine Grinding at Supercritical Speeds. By R. T. Hukki (Mining EnGineERInG, May 1958). Eq. 9, page 588, should be as follows: T , c, (a — 6') n D Ltph On page 584 of the article the captions for Figs. 4 and 5 have been placed under the wrong illustrations and should be interchanged.

Jan 1, 1959

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,' in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts' method and a quenching method. In the first method, the Sieverts' technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts' Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,' to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts' apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier's analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964