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By F. H. Parsons

At the time that converting or bessemerizing of copper matte first began to be practiced by the smelters in the copper industry, converters were lined by tamping the flux, usually siliceous ore, into the steel shell. About 1910, practice in several plants had demonstrated the superiority of a basic lining of nonfluxing material and the addition of flux through the mouth of the converter. Adoption of the new method by nearly the entire industry followed. Basic linings are made of refractory "magnesite" brick manufactured, usually, from imported dead-burned magnesite. Either the linings are laid up in the shell dry or the bricks arc bonded with some mortar dictated by the preference of the user. Foreign, usually Austrian, magnesite was the main source of supply for these bricks, although there were domestic sources, but it was not until costs began to rise a few years after the first use of basic linings that these domestic sources were investigated to any great extent. Exigencies created by the World War necessitated the use of the domestic magnesite during this period, but the brick manufacturers reverted to the use of the foreign product after the war, because the impurities therein made a brick with a better fire bond than the purer domestic magnesite. Therefore the domestic product became available at a favorable price for any metallurgical process that permitted its use. The United Verde converting practice using magnesite linings has resulted in a high consumption of magnesite because of the zinc content of the low-grade matte. It was realized that the cost of these linings represented a large portion of the cost of converting, and an investigation was started to find means by which these costs might be lowered. In the neighboring state of California rather pure magnesite was being mined and treated for the market. The product, however, was purposely made to simulate the dead-burned grain magnesite product from foreign sources by the addition of fluxing impurities before burning. It was learned that this dead-burned California grain magnesite could be laid down in Arizona at a price one-third that of the same tonnage of "magnesite" brick manufactured from foreign magnesite. It was also learned that at least one California producer was ready to supply the market with periclase, which was a grain magnesia produced by burning the

Jan 1, 1934

By C. Kolm, E. P. Warekois, S. A. Kulin

MUCH insight has been gained into the nature of the cold-worked state of metals in recent years through the use of modern X-ray techniques. These methods have revealed the existence of stacking faults together with regions of high internal strain and have provided means of measuring the atomic perturbations in plastically deformed metals. In view of the recent increased interest in the solid state, it is desirable to extend these techniques to the study of lattice imperfections introduced into semiconductors during plastic deformation. It is of particular interest to compare the state of imperfection sustained by metallic bonding with that sustained by the covalent bonding found in semiconductors. A knowledge of the imperfections which can exist in semiconductors is important from both a theoretical and a practical point of view since they can greatly influence many of the physical properties. In order to determine the possible existence of stacking faults in covalently bonded structures, precise measurements were made of the diffracted peak positions of plastically deformed germanium, gallium antimonide, and indium antimonide. These measurements were based on the theoretical treatment of Paterson1 and are similar to those employed by Warren and warekois2 in their studies of deformed a brass. In addition, diffraction peak profiles were measured on the annealed and plastically deformed materials in order to obtain information concerning the distribution of internal strains through the use of the Fourier methods developed by Warren and Averbach.3 EXPERIMENTAL PROCEDURES AND TECHNIQUES Because of the room-temperature brittleness of the semiconductors studied, it was necessary to plastically deform the materials at elevated temperatures. The brittle-ductile transition temperature ranges of GaSb and InSb are sufficiently low to permit hot-filing operations. Therefore, high-purity, polycrystalline GaSb and InSb were filed in an argon atmosphere at 400' and 300°C, respec-

Jan 1, 1959

By Arthur Fleischer

The Kalunite process+ for the production of metal-grade alumina from alumina-con-taining ores is applicable, considered from a general point of view, to any aluminous raw material that can be converted to potassium alum or equivalent normal alum. This result of modern technology has been the subject of a continuous study and development since 1929, on a laboratory and test-plant scale, with initial emphasis on the utilization of alunite as the raw material. The research and developmental program was carried out by the Kalunite Company and its successor, Kalunite, Inc., an affiliate of the Olin Corporation of East Alton, Illinois. The process is now approaching the time for a major test in its history with the completion of construction of a plant having a capacity of IOO tons of alumina per day in Salt Lake City for the conversion of Marysvale, Utah, alunite ores to alumina and potassium sulphate. The Salt Lake Alumina Plant is a Defense Plant Corporation project. Production of Aluminum: The known existence of alunite deposits, especially in the Marysvale district, furnished the motive for the original inquiry into the utilization of this raw material for aluminum production. The deposits in this region were actively explored during World War I and utilized for the production of potassium sulphate, an essential fertilizer, of which a shortage of monumental proportions then existed. Up to the twentieth century—for alunite is a mineral with an ancient history—it was used in Europe and in China as a source of potassium alum. It never had been used successfully in this country as a source of oxide for reduction to metal. Although the known reserves of this ore, which undoubtedly will be greatly expanded with a commercial outlet for this ore, are recognized to be sufficient for only a part of the present-day needs of aluminum, it has a definite place in the aluminum industry. Academically it points the way for future raw materials. The aluminum industry has undergone a remarkable growth in the past few years as a result of defense and war requirements. Its expansion in many ways has been beyond belief and prediction, both in volume and location. This wartime status of the industry has accelerated the consumption of bauxite to such an extent that a re-evaluation of the raw material reserves for the future peacetime industry and for eventual wartime reserves is seemingly of concern. The generally accepted picture of bauxite ore reserves in the United States, especially in raw material suitable for treatment by the Bayer process, focuses attention on other possible sources of raw material of metal-grade oxide. The perspective for the development of a suitable process may have changed in the interim since the original work by Kalunite, but the ultimate goal is the same.

Jan 1, 1944

By T. M. Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the 'active masses' of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. dC Thus----— kc [1] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of un-floatable mineral. Hence the first order equation is It has been proposed by various workers1-' that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris- as discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1953

By T. A. Rickard

The lode-formation of the Bendigo gold-field was described in a former paper.* It presents a striking identity of arrangement with the general geological structure of the region, which is one of comparative simplicity. The alternating beds of slate and sandstone which constitute the prevailing country-rock have been extremely contorted ; yet notwithstanding their highly developed cleavage it is possible to discern in their structure the evidences of original sedimentation. Along the crests of the waves which are the axes of anticlinal folds occur bodies of gold-bearing quartz, of great economical importance, which the miners have appropriately termed " sad-

Jan 1, 1894

By W. W. Lowry, G. C. Eggleston, W. E. Keck

THE potential iron ores of Michigan can be classified from the stand- point of the predominant impurities into siliceous, sulphurous and phosphorous ores. Research on the flotation of each of these classes of ore was carried out in the following manner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly pure state. There are two varieties of the mineral-specular hematite and massive hematite. The latter is the principal variety, but the former is an important mineral of iron in some of the potential ores. Because of this condition, flotation research was performed with both varieties. This research consisted essentially of: (1) a survey of the literature on hematite flotation, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a proprietary frother and oleic acid or other soluble oils2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1937

CHARGING of an open-hearth heat is begun as soon as possible after the previous heat has been tapped. Ordinarily, about 40 min is required to drain and dress the furnace hearth, make up the taphole, and perform routine repairs of the banks. Repairs to the upper back wall and to the front wall and jambs can ordinarily be done while the first scrap charge is being heated and are therefore allowed to wait in order to save furnace time. Any major repairs required on the hearth or other parts of the furnace necessitate longer delays because such repairs must be made while the furnace is empty. Although charging practice varies considerably in detail with the type and proportions of scrap and iron used, many factors are common to all varieties of charge. Such general considerations are dealt with first. CHARGING EQUIPMENT AND STOCK HANDLING The physical equipment available for loading and weighing the stock, transporting it to the furnace, and charging it, may have a major effect on charging practice. Limestone, scrap, and all other solid melting stock are charged mechanically by means of equipment illustrated in Fig 2-1. The charging of hot metal is shown in- the background of this figure. Mechanical equipment and plant layout for stock handling are described in Chapter 1. It is generally desirable to charge the scrap about as fast as the physical volume can be put into the furnace. Charging scrap that is too heavy or adding the charge too rapidly (less than 45 min) may be detrimental to melting rate because of excessive chilling of the entire furnace system and also because of poor conduction of heat to the lower layers in the furnace; but the more common problem is the reverse one of charging light scrap fast enough to maintain a normal heat time. A limiting factor may be the height to which the scrap may he piled in the fur-

Jan 1, 1964

By J. A. Hutcheson

NO one questions that it is technically possible to achieve the controlled release of atomic energy in a form that can be converted into heat or electricity. However, before this is actually an accomplished fact a great amount of work must .be done. This work falls into two general classifications: research and engineering development. At present a research program is under way in this country, co-ordinated and directed by the Atomic Energy Commission, which, as time goes on, will uncover fundamental knowledge of this new science that is essential before industrial applications of atomic energy are practical. Undoubtedly therefore, as the store of available knowledge increases, a time will come when answers to the many questions relating to practicality of atomic energy in industry can be determined with reasonable certainty. That the application of atomic energy in industry will eventually be proved practical is assumed. What then are the engineering problems that must be solved before the first practical electric power generating station can be built?

Jan 1, 1948

By C. F. Smart

Since their comparatively recent development, the alloys of cadmium with silver and copper or nickel, and of cadmium with nickel alone, have been used somewhat extensively as liners for connecting rod bearings and main bearings of internal-combustion engines. In applications where, owing to high bearing loads and elevated operating temperatures, the life of bearings made from tin-base or lead-base alloys has been undesirably short, cadmium alloys have demonstrated considerable advantage. In applications where, because of deflection of the crankshaft or bearing supports, copper-lead bearing metals have resulted in scored shafts, cadmium alloys have been operated successfully. The somewhat serious drawback to these alloys in bearing service has been that they, in common with copper-lead and certain lead alloys, are susceptible to corrosion in the presence of lubricants containing organic acids. These acids may be fatty acids (such as oleic acid) derived from animal or vegetable oils that sometimes have been compounded with engine lubricants, or they may be compounds of an acid nature developed by the oxidation of some petroleum oils under operating conditions. The result of such acid attack on bearings is illustrated by the photograph, Fig. 1. The petroleum oils that are most readily oxidized to a corrosive condition, and the operating conditions under which such oxidation most readily occurs, are now rather well known among the technical organizations of both the petroleum and automotive industries. While means have been developed for inhibiting petroleum oils against such acid formation, the knowledge that this condition may be encountered has been a factor in restricting the wider use of cadmium alloys as engine bearings. It has appeared, therefore, that their value and use would be enhanced if they could be made corrosion-resistant to a degree compatible with the most severe operating requirements. Investigation, undertaken with this in view, indicated that the addition of fractional percentages of the metal indium to the cadmium bearing

Jan 1, 1938

By C. E. Sims

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

Jan 1, 1948

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By Murray Kaufman

Using en; 41 for a base alloy, 15 modifications were made in sheet form. The elements Al, Ti, C, Mo, Co, and Cb were varied. The effects on the phases formed and their temperature dependence, the aging characteristics, tensile and stress-rup- ture properties, and weld cracking were determined. The A1-Ti content and balance is the most important factor influencing the major sCrengthening phases [Ni,Ti and Ni,(Al, Ti)] and, consequently, mechanical properties. THE mechanical properties, fabricating and joining characteristics, dimensional stability, and so forth, of alloys containing secondary phases are largely determined by the phases present, their distribution, and their temperature dependence. The phases in the basic ternary and quaternary Ni-Cr-Al-Ti combina- tions have been investigated thoroughly.'* The phase behavior of many commercial nickel-base alloys has been determined also. In some cases, for example U500, 5 the effect on mechanical properties has been found. However, little systematic work has been done to clarify the action of each of the important alloying elements in controlling the phases formed in complex commercial alloys and their behavior. The effect of molybdenum on the carbides formed in M252 was investigated by Beattie and verSnyder.6 Application of the results provided by that work

Jan 1, 1963

By John L. Ham, Robert M. Parke

THE melting point of molybdenum is 2625° ± 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. 1, 1944, to Aug. 31, 1945, the project was under the supervision of the National Defense Research Committee, Division One. In peacetime, too, there are needs for molybdenum, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. FIRST PROCESS FOR MELTING AND CASTING MOLYBDENUM The maintenance of a temperature greater than 2625°C. in a space large enough to melt several pounds of molybdenum may involve the loss of heat at a very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum. In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1946

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 C. E. Sims

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

Jan 1, 1948

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG's ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid' have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey' presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By J. M. Cases

Study of the normal interaction between flotation collectors and the silicates through measurement of the electrokinetic potential carried out by the streaming potential and flotation recovery methods indicates that the interaction is wholly 07 partly of electrostatic origin. In some cases, it partly consists of the chemical affinity of the polar head of the collector for the active surface sites. Reagents composed of a polar head and a paraffinic chain and forming micelles in solution were used as flotation collectors. They are sodium dodecylsulfate (anionic collector) and dode-cylammonium chloride (cationic collector). The adsorption isotherms on biotite of alkylamine chloride having 10 to 18 carbon atoms in their chain all show a sharp change in slope relevant to the condensation of alkylammonium ions into bidimensional phase.1-1 Condensation is possible because of the relative homogeneity of the adsorbing surface and of the very strong lateral binding forces through Van der Waals type bonds in the adsorption layer. The different isotherms are seen to coincide when, instead of the equilibrium concentration, the under-saturation ?µ = kT In C/C, is plotted in abscissa, C representing the concentration of the solution with which the adsorbed layer is in equilibrium and C, the saturation concentration of micelles in solution or. critical micellar concentration. More particularly, the undersaturation ?,u1*, corresponding to a surface coverage 6 of 0.5, is equal to Since silicates immersed in aqueous solutions show a surface charge which is a function of pH, it is of primary importance to study the influence of this parameter on the adsorption of collector ions acting as Strong electrolytes in the pH range where they are utilized. The aim of this present paper is to determine by studying electrokinetic phenomena and recovery curves effectuated with a cationic collector and a anionic collector, the nature of the normal adsorbate-adsorbent interaction. Tables 1 and 2 sum up part of the results previously obtained'H11 for the determination of the point of zero charge of the silicate studied by the streaming potential method. Throughout the remainder of this paper, the surface charge will be considered positive for all values of pH below the point

Jan 1, 1971

By George Sachs, S. M. Clark, George Espey

he tendency of a commercially drawn cartridge case to crack in the mercury test and the relation of cracking tendency to residual stress retained after drawing were studied. The fourth drawpiece (next to the final) of caliber 0.30 cartridge cases produced by Frankford Arsenal were selected as test pieces. These exhibited an exceptionally high cracking tendency, making a detailed study possible. To obtain fast cracking in the mercury test, about 0.0015 to 0.003 in. must be removed from the wall thickness of the drawpiece by pickling, and it must be subjected to the mercury test immediately after washing. Removal of the adhering mercury by annealing and subsequent squeezing of the case in a vise was used to reveal definitely the presence or absence of cracks. Various lots of apparently identically fabricated cases were shown to possess a different cracking tendency. Machining off or boring a hole in the base gradually reduced and eventually eliminated the cracking tendency. On the contrary, shortening of the wall (body) reduced the cracking tendency only if the wall became so short that the cracking zone was directly affected. By boring out the base and pickling from the outside and then splitting the resulting rings, it was possible to determine the approximate stress distribution in the base and in the adjacent part of the wall. Small compression stresses were present in the core and the major part of the base, while the surface of the base and the adjacent wall contained high circumferential tensile stresses. On the contrary, the wall when parted from the base contained only insignificant residual stress. The conception is advanced, that the stress distribution in a drawn cartridge case corresponds fundamentally to that of a tube (wall) shrunk on a disk (base). Such a stress distribution results from the tendency of the base to recover elastically by an increase in diameter from the biaxial compression during drawing while the wall exhibits little tendency to change its diameter after progressing through the die. This is confirmed by measurements which show the base diameter to be slightly larger than the wall diameter.

Jan 1, 1945

By E. Swartzman, G. C. Behnke

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button. A method of analysis to be satisfactory not only for a scientific laboratory but also for use in industrial control laboratories under varying conditions should employ equipment which is rugged, easily calibrated, and readily replaceable by standard materials. Gas is not universally available as is electricity, and it is generally easier to calibrate and control a simple electric furnace or heater than a gas burner, the voltage not usually fluctuating to the degree that gas pressure does. Quartz crucibles are fragile, and the size specified in the test is not normally used for any other purpose in the laboratory. Although more expensive, the 15-cc platinum crucible, available in all laboratories where volatile matter in coal is determined by the standard ASTM method, is sturdy and standard and easily replaced. Because of these considerations, a modification of the standard method has been developed which employs a standard laboratory 350-w cone heater and standard 15-cc platinum crucibles. The results of numerous tests conducted with such apparatus show conclusively that the free-swelling index values as judged by the buttons produced with this equipment are exactly the same as those obtained by the standard gas burner method. Thus it is suggested that this electric cone heater method employing standard 15-cc platinum crucibles be considered as an alternative to the ASTM method, Designation: D720-46. The free-swelling index of coal is determined by means of the ASTM method, D720-46. This method, which is an adaptation of the crucible swelling test for coal of the British Standards Institution, consists of heating 1 g of coal in a special covered quartz crucible in a regulated gas flame for a period of not less than 2.5 min in which time the temperature of the inner surface of the bottom of the crucible reaches a temperature of 82025°C. The residual coke button is then compared in size and shape with a series of standard profiles shown in Fig. 1 and designated by number from 1 to 9 in increasing order of size. As the method is empirical, it requires rigid standardization of the apparatus and repeated calibration of the gas burner. The dimensions of the low form quartz crucible recommended must be rigidly adhered to as small variations in diameter or wall thickness result in variations in the rate of heat transmission and thus in the resultant size and shape of the coke button. The gas burner must be calibrated almost every time a new set of determina-

Jan 1, 1952

By Robert W. Thomas

During the past 20 years the advantages of reinforced concrete as a substitute for timbering in so-called permanent mine openings have been fully recognized, and its use has become almost general practice in the larger mines. The term "permanent mine openings" is used advisedly and is assumed to embrace such openings as ventilation shafts, material shafts and main hoisting shafts, with their adjacent stations, ore pockets, etc. In the concreting of such openings, the actual cost as compared with that of timbering has been of secondary consideration, the support of large openings, elimination of fire hazards, and prevention of interruptions to production being the primary objectives. The ultimate economy, however, of lining such openings with concrete when they are to remain in use during the entire life of the mine, and especially when they are in bad ground, will seldom be questioned. During this 20-year period there have appeared in engineering publications a number of interesting articles on the use of concrete in mines, nearly always describing some specific project of major proportions, such as the concreting of ore pockets, large stations or main hoisting shafts. Such articles are unquestionably of interest, since the projects require considerable engineering thought, not only in the method of excavating large openings, but in their engineering design as well. Concreting of main hoisting shafts, particularly when this is done with the least possible interruption to production, provides some interesting problems. The concreting of haulage drifts of the dimensions commonly found in mines, on the other hand, soon develops into a routine operation, therefore it is with some hesitancy that the author attempts to prepare an article on this subject. The writer can recall only one article on the concreting of mine haulageways, although several articles have been written concerning the concreting of tunnels considerably larger in dimensions than those required in general mine practice.' From the scarcity of articles on the subject, it would seem that the concreting of haulage drifts is still far from being considered general

Jan 1, 1937