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By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

By Fred W. Stiefel

To open the Fisher Hill mine of the Republic Steel Corporation, it was necessary to sink an inclined shaft into the rock and excavate stations, drifts, and ore pockets. This inclined shaft, or slope, q ft. 8 in. high by 28 ft. 2 in. wide, has compartments for two 5-ft. gauge ore-skip tracks of 120-lb. rail, one 5-ft. gauge man-skip track of 60-lb. rail, a concrete stairway, and service pipes consisting of a 12-in. compressed-air line, an 8-in. pump-discharge line, and a 4-in. water-supply line. When we were requested to investigate the work, the progress being made (by another organization) amounted to only 2 ½ ft. advance in 24 hr. We reported that progress of at least 6 ft. per day could be made. As a result, the Defense Plant Corporation, through the Republic Steel [ ] Corporation, entered into a contract with us to sink the shaft. The contract contained a penalty and bonus clause predicated upon an advance of 150 ft. per month. The average advance was 7.8 ft. per day; that in the best six-day week was 60 ft. and that in the best month, 215.5 ft. in 25 working days. The drilling was performed by 3 ½ -in. wet drifter drills mounted on five 8-ft. columns (see accompanying illustration). Even though a full-face drilling and mucking operation is customarily desirable, the steep slope, with the accumulation of water and fine debris at the face, made a modified heading and bench operation preferable. The heading and bench were of equal height. The five columns, instead

Jan 1, 1945

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, 'iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other *producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since her particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely he kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1948

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, 'iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other *producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since her particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely he kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1948

By Earl H. Miller, Henry H. Bruhn

COMMERCIAL beds of sylvite ore were discovered by the Snowden & McSweeney Co. while drilling a wildcat oil well some 25 miles northeast of Carlsbad, N. NI., in 1925. After a preliminary core drilling program the U. S. Potash Co. sank a 1060-ft shaft within 4 miles of the original discovery. This shaft was in an isolated location in a sand desert area with only the roughest of dirt roads connecting it with the neigh- boring town of Carlsbad some 21 ½ miles west.

Jan 6, 1954

Albert Sauveur writes, on Apr. 16, 1918, while the German offensive was at its height, as follows: "In spite of the German guns and air raids we are all in good health and spirits and shall leave Paris only as a last extremity. Our unlimited confidence in Foch, however, makes us believe that it will not be necessary. I trust that everything is well with you at the Institute." Harold Whittingham entered the active service with the heavy artillery in England at the beginning of the war and has been fighting in France since February, 1915. He now holds the rank of Major. On Dec. 17, 1917, after being wounded, he was taken prisoner by the Germans, and, so far as is known, is still in a prison camp in Germany. Charles W. Wright, who is a Captain in charge of the work of the American Red Cross in Sardinia, Italy, writes that the service there is giving aid to about 80,000 soldiers' families and is upholding the good repute of America in that place. W. S. Holloway in 1914 joined the Sportsmans' Battalion of the Royal Fusiliers as a private, but is now a Lieutenant in the Royal Engineers, Mining Corps. He received the Military Cross while mining at the Front in France. A. L. Queneau writes the following interesting account of his experience of the war. Several letters from Mr. Queneau have been published

Jan 6, 1918

By Richard R. Parizek, E. Scott Blair

Numerical modeling of ground water flow systems can be used to help analyze many practical problems encountered in the mining industry. Numerical models can be used to predict ground-water seepage rates into surface mines, shafts, and other large excavations; to predict water-level changes under adjacent properties; and to predict the effectiveness of various deep-well dewatering schemes. As with any model, the results from a numerical model are limited by the quality and quantity of data, and by the restrictions of any simplifying assumptions. A case study is presented that shows how a numerical model was used for engineering purposes to help analyze the hydrologic impact of a proposed open-pit mine by Predicting changes in the dewatering rate caused by the lateral growth and deepening of the mine and by predicting the effectiveness of various deep-well dewatering schemes.

Jan 1, 1982

By E. L. Kapfer

A preliminary description is made of the field of automation and optimization of the oxygen blast furnace process. The concept of static and dynamic process control is illustrated. After a short general description of all factors concerning the optimization of this process, a learning system is derived which gives better results than models previously used. This learning or self-adaptive control system uses statistical methods with exponential aging of process data and requires derivation of multi-variable functions of the process for which measurements can be made available. The practical application of this new procedure and of additional measuring instruments are discussed, and results obtained in plants using the adaptive control system are described. A survey of European steel plant automation using the Siemens technique is presented.

Jan 1, 1969

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,3 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 8, 1915

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946

By L. G. Schulz

THE possibility of using reflected X-rays to produce images of crystals was explored by Barrettl who developed simple experimental procedures for X-ray microscopy and who showed by numerous examples the great range of information that could be made available. In his method characteris radiation is used to produce an image of a limited area of the sample on fine-grained film, this image subsequently being enlarged approximately X100. A somewhat different method will be described here;' white radiation from a fine-focus X-ray tube-"' is used to produce an image of a relatively large area of a single-crystal surface. part of the sample; therefore, white radiation is needed. The resolution in the image formed on the photographic film will depend on the size of the focal spot of the X-ray tube. If the sample is made

Jan 1, 1955

By Francis M. Walters

THE problem of making iron-manganese alloys of scientific purity is a rather difficult one. They cannot be prepared in air because of the readiness with which the metals oxidize at the temperature of melting; and they cannot be prepared in vacuum because of the, high vapor pressure-of- manganese. The very property of: manganese which permits it to be purified interferes with the utilization of the best method of making pure alloys. Accordingly, it is necessary to use a gas atmosphere which will not affect the-properties of the alloys. The gases available for the purposes are hydrogen; helium and argon. Nitrogen forms intermetallic compounds with manganese very readily. Hydrogen, while valuable as a deoxidizer and having the advantage of being comparatively cheap, is explosive over a wide range and, has a rather high thermal conductivity. Helium is reported as, costing little but is difficult to secure at a reasonable price and also has a conductivity nearly as high as hydrogen. Since argon has a sufficiently low thermal conductivity, it has been selected for use in one induction furnace for melting, under a controlled, gas atmosphere, in spite of its cost, which is so high (70 cents to $1.50 per cubic foot) that it must be stored and purified.. Such a gas atmosphere-as argon makes necessary the use of the, high-frequency induction method of heating. This involves, a non-metallic container for the gas; .which is most conveniently of fused quartz or glass. The next

Jan 1, 1929

By R. L. Rickett, N. C. Fick

Despite the large volume of literature on alloys of iron and silicon,' there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By N. C. Fick, R. L. Rickett

Despite the large volume of literature on alloys of iron and silicon,' there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By W. R. Bull, J. R. Roos

A method is described whereby the true financial value of each constituent of each concentrate can be calculated. Each value is then compared with what this value would be in a perfect separation. The difference in each case represents the loss incurred by each aspect of an inefficient separation. The relative magnitudes of these losses indicate those avenues of plant investigation and research that offer the highest potential reward. The metallurgical efficiency of a concentration operation is difficult to express because there are two criteria of performance, namely, grade and recovery. Neither of these alone gives any indication of the effectiveness of an operation and, if they are combined in some formula, it must be empirical and unreliable because of many external factors. Since milling is an operation performed as one step in the most profitable overall method of producing a metal or other end product, the main objective of mill operation should be to make a maximum contribution to this maximum profit. When concentrates are sold to custom smelters, the income from the operation, and the costs, may be calculated. When concentrates are further processed by another division of the same company, and there is no formal financial relationship between, say, the milling and smelting divisions of the company, the mill superintendent's job is less well defined. But even so, if the mill superintendent works as though he were selling his concentrates, and uses reasonable, if fictitious, conditions of sale, then he can get a good indication of the effectiveness of his operation by calculating his "Economic Recovery". ECONOMIC RECOVERY This is a method used as a basis of operation by several mills and has been described in the literature. Very briefly, the "standard" of operation is taken as that of a mill separating the ore into perfectly pure concentrates with 100% recovery of each mineral in its respective concentrate. For example, a 4%Pb, 4% Zn ore (galena and sphalerite), would provide a lead concentrate weighing 4.62% of the feed and assaying 86.6% Pb and a zinc concentrate weighing 5.97% of the feed and assaying 67.1 % zinc. These perfect concentrates are (hypothetically) shipped to the appropriate smelters, freight and treatment charges and payments calculated, and the net return obtained. This is the optimum financial return for the operation of the mill and is used as the standard. Now the return for the actual, real-life, mill operation is calculated in the same way, and the ratio of the two is termed the Economic Recovery. Many additions and modifications may be made in any particular case. For example, if the zinc mineral is marmatite, the optimum grade of the zinc concentrate may be set lower than 67.1%. If silver is present, it will be recovered 100% in the lead concentrate in the perfect operation. Similarly, cadmium will be recovered 100% with the sphalerite. Mr. Weiss' paper' mentions a case where, because of extremely fine intergrowth between the valuable mineral, chalcocite, and pyrite, the optimum grade of copper concentrate was taken as 45% Cu instead of the theoretical 80%. Each operation will present its own possibilities in this way.

Jan 1, 1970

By J. Th. G. Overbeek, R. Schumann, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.1-3 Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles.

Jan 5, 1954

By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

By J. E. Johnson

The description of the machine which coilstitutes the subject of this paper is best iutroduced by a statement of the conditions which led to its construction, which may be briefly given as follows : The ore handled at the plant to be here described* is of the variety sornetimes called by those familiar with the brown ores of the South, " Mountain," as distinguished from the " Lime-

Jan 1, 1899