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By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By Louis R. Hodell

WHEN the drilling of an oil well is completed a permanent opening from the reservoir to the surface must be provided. This is done by lining the hole with pipe, commonly known as casing. In the past, all but a small amount of casing has been run in the hole and joined by threads and couplings. Recently, however, in California, Texas, and Oklahoma, there has been a definite tendency 'to adopt -the welded joint for the following reasons: (1) Plain end casing for welding may be bought for 15 per cent less than thread-and-coupled casing; some of this is offset by the cost of welding the pipe in the hole but a respectable net profit remains.

Jan 1, 1937

By W. F. Stowasser

downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in cooperation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace. Process Description The first of two process steps incorporates the art of balling and prepares the concentrates for burning. The second step consists of burning the green balls on the grate machine to the hardness required for shipping and handling purposes and for reduction in blast furnaces, see Fig. 1. Facilities are provided at the pilot plant to receive carload quantities of concentrate. The concentrates are loaded into a 50-ton bin direct from railroad cars. Because of the variable moisture content of the concentrates after shipment in an open railroad car it is necessary to repulp and refilter the concentrates to maintain a uniform and proper moisture content for the balling operation. Concentrates are conveyed to slurry tanks, and the slurry, at 50 to 60 pct solids, is pumped to a 4x4-ft drum filter. The filter provides feed of uniform moisture to the plant. Magnetite concentrates are normally filtered to produce a cake containing about 10 pct moisture, a necessary requirement for the following balling operation. The filtered concentrate is conveyed to a rotary bin table feeder which acts as a surge bin for the filter cake and delivers a steady flow of concentrates to the balling drum. It is often desirable to make additions to the concentrates as they are fed to the balling drum. These additives, such as bentonite, increase the strength of the finished green pellet and improve ballability of the concentrate. A vibrating feeder supplies additive to the feed belt, and the additive is mixed with the concentrate in the balling drum. The balling drum, shown in Fig. 3, is 8x3-ft diam. An oscillating cutting bar maintains the lining in the drum by trimming off the buildup of excess concentrate as it forms. The drum is operated in closed circuit with a lx4-ft rod-deck vibrating screen. Undersize pellets or seed pellets from the screen are returned to the balling drum until they grow to the desired size. Size of pellets is controlled by the opening in the screen deck. The formation of pellets in the balling drum is affected by many variables. Some of these are: the size distribution of the feed, the particle shape of the concentrate, the feed rate to the drum, the moisture in the concentrate, the speed of rotation of the drum, the slope of the drum, and the type of trimming obtained with the cutting bar. In this process, attempts are made to control the pellet size within the limits of % to 5/8 in. diam. The screened oversize pellets are conveyed under a coal feeder where sufficient powdered coal is added to the belt to produce desired results in the burning process. The top size of the coal successfully used has been 20 mesh, and anthracite was used in the test program. Fig. 4 illustrates the vibrating screen and the coal feeder. The pellets and free coal are conveyed together to the 5x3-ft diam- reroll drum that rolls the coal onto the surface of the pellets. This drum is also equipped with a cutting bar. The prepared pellets, containing bentonite, water, and surface coal, are elevated to the traveling grate, which consists of a continuous strand of 37 pallets. Each pallet, with a grate bar area 2 ft wide by 1 1/2 ft long, has 14-in. high side plates, Fig. 5. Feeding and distribution of the green balls to the grate is handled by a short conveyor which oscillates back and forth across the 2-ft width of the grate. An adjustable vertical plate located several inches in front of the head pulley of the oscillating conveyor controls the height of the bed and levels the moving bed of pellets. This method of feeding prevents segregation of various size pellets as well as fines and produces a uniform, permeable bed. The pallet train moves under the furnace and across four windboxes, located beneath the pallet frames, see Fig. 2. As the green pellets are deposited on the grate, partial drying of the pellets begins over a 2-ft long updraft windbox. The low temperature air reduces the moisture in the pellets in the lower level of the bed and this operation is essential to prevent sagging of the bed during later stages of the Process. The air used for this drying is recuperated from cooling the pellets on the grate, and supplemental heat, required for starting the Process, is obtained from an auxiliary burner. The pellets are then moved by the grate into the furnace and over an 8-ft windbox, designated as the downdraft waste windbox. Products of combustion are exhausted from this windbox to atmosphere. The furnace, shown in Fig. 6, is constructed with three chambers to provide downdraft drying, preheating, and ignition, respectively, to the pellet bed as it passes through. Overall length of the furnace is 5.57 ft; however, the exterior wall ends may be moved to reduce the length and also adjusted to Obtain the bed height desired, The drying, preheating, and ignition sections of the furnace are supplied with medium temperature

Jan 1, 1956

By E. Tulcanaza

The practical significance of the in situ grade variability is usually neglected. Although recognized, often times it is either ignored or just considered as a vague guideline in many of the decisions dealing with exploration, reserve estimation, and mine planning. This paper stresses the significance of grade variability for exploration and mining, and illustrates its liaison to the structural features of the ore deposits, as well as to the mining parameters used for mine extraction. Some geostatistical results obtained from a silver mine, tungsten mine, and copper mine in South America are discussed.

Jan 1, 1985

By Magnus Troilius

INTRODUCTION BY C. P. SANDBERG. SINCE the discussion On steel rails in America has forcibly drawn attention to the value of chemical analysis, if not as a necessary stipulation, at least as a guide to control the usual mechanical tests, some doubt has been thrown upon the accuracy of the analytical results Obtained by different chemists. To any One having the least acquaintance with chemistry., it is quite clear that if exactly similar results are to be obtained from the same borings of steel, exactly the same methods must be used by the different analysts. Hence the necessity (if complications are to be avoided) of establishing what I may call standard or normal methods, to be used both by the inspectors and by the chemists at the works. Remembering that the application' of chemistry to steel-rail inspection is yet in its infancy, it is of great importance to possess a perfect acquaintance with the best methods in use. Being myself a grateful pupil of Professor Eggertz, of the School of Mines in Sweden, it Occurred to me, two. years ago, that I could not do better than start a laboratory of my. own, and engage One of his pupils, Mr. Troilius, for the purpose of analyzing the steel borings from mechanically-tested rails, so that I might thus Obtain without delay thoroughly accurate determinations. Moreover, in Order to carry on the, operations in perfect accordance with the methods used at the steel works in England and Germany, where I had to control the manufacture, I deemed it desirable to allow Mr. Troilius to go through a course of training at these works; and I gladly seize this opportunity of expressing my grateful acknowledgments to several works in England and in Germany for affording every facility for such an exchange of information as was found necessary in arriving at the best analytical methods to be used.

Jan 1, 1882

By Paul Tyler

THE ferroalloying elements are connecting links between the steel industry and the nonferrous metal industries. Although ferroalloys are distinctly nonferrous themselves, they serve the steel industry either in the manufacturing process or in modifying the product-in some cases so that it may compete in the markets with nonferrous metals. Of the 92 elements generally accepted by chemists as constituting the primary building blocks of matter, all but the very rarest have been investigated with a view to employing them in steel manufacture. The surprising thing is that so few have been found commercially acceptable. Despite the relatively small number of elements involved, the employ-ment of alloys in steelmaking is one of the most complicated and probably one of the least well understood of modern industrial enterprises. A great deal has been written regarding the action of individual elements and a profuse and somewhat acrimonious literature covers pretty much the whole field of ferroalloy ore supplies. In the middle ground between the miner and the steelmaker developments are less carefully watched by most observers, and except for an occasional description of the technique of some conversion process or the tariff hearings in Congress, very little is said about them. The purpose of the present paper is to describe in relatively nontechnical terms this highly complex industry and to study its relations to our national progress.

Jan 1, 1933

By J. Van Steveninck, A. C. Pols, R. Feenstra

In the course of time, an increasing number of investigations on jet cutting all kinds of material, such as rock,1,2,3 metal,4,5 and wood6 have been reported to serve various applications. A number of papers have been published on these subject, 7,8,9 some of which refer to jets purposely containing abrasives, termed 'jetted particle drilling'.7 Since such abrasives complicate fluid handling considerably and do not appear to be absolutely necessary for making holes, only conventional drilling fluids have been considered. A large part of our investigation has been performed with the aid of three laboratory-type drilling machines, which permit tests on both micro-bits (1 ½ in. ) and full-scale bits (6 ½ -9 5/8 in. ) . In view of the application of jets in deep holes, care has been taken to simulate hydrostatic pressures as they exist in the field on the hole bottom. These have been found to have a major effect on the bit-penetration rate for various drilling fluids.

Jan 6, 1974

By Edgar Stansfield

ONE of the most striking features of the coal series passing from peat through brown coal, lignite, etc., up to anthracite is the gradual reduction of moisture content with the increased coalification of the original plant material. Thus drained peat from a bog may contain 90 per cent water, brown coal contain 50 per cent, lignite 30 per cent, while a bituminous coal may contain only 1 per cent moisture. Moisture, therefore, is one of the important factors to be considered in coal classification, especially with the lower rank coals. With bituminous and higher rank coals the moisture content is less satisfactory for classification; it may even pass a minimum value and then increase with increasing rank to anthracite and superanthracite. Coal in an undisturbed seam contains moisture which is an integral part of the coal, but it may also be wet with free, underground water percolating through the seam. Only the former must be considered in evaluating the moisture content of the coal for classification purposes; this will be called the "true moisture" of the coal. When the seam is mined and sampled the sample taken may show the true moisture; on the contrary, it may contain in addition free mine water or, especially in dry, well ventilated mines, it may contain less than the true moisture. Coal contains unstable organic compounds which may decompose, with the production of moisture, when the coal is exposed to air at ordinary temperatures, or is heated with or without exposure to air. The potential moisture of a coal therefore is higher than its actual moisture. The lower the rank of the coal, the greater its instability, as a rule, and the greater the care necessary to avoid oxidation or decomposition in any investigation of moisture content. The majority of coal workers have preferred, on account of the difficulty in evaluating the true moisture of a coal, and for other reasons, to classify coals by analyses calculated to the dry-coal basis. A number of workers familiar with lower rank coals have recently insisted that the classification of such coals can be satisfactory only if analyses on the moist-coal basis are employed. The moisture-holding capacity of coal is therefore intimately connected with coal classification, and in this paper a procedure is outlined for determining the true moisture of a coal.

Jan 1, 1932

The Library of the above-named Societies is open from 9 A.M. to 9 P.M. on all week-days, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining-maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable-shape. The members of the Institute can be of service to the Library by forwarding copies of mining-reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and assurance is given that most careful service will be rendered to them.

Jan 2, 1914

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for, this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators 1.2.1 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By E. R. Parker, C. F. Riisness

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By C. F. Riisness, E. R. Parker

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By M. B. Ramachandra Roa

This paper records the results of the earth resistivity surveys made in the Godavari River in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented. Introduction The Government of Madras has under consideration the Ramapadasagar project which is estimated to cost some Rs.660,-000,000 (about two hundred million dollars). The most essential feature of this project is the construction of a high dam across the Godavari near Polavaram for impounding the waters of this great river of South India, whose maximum discharge is 2 million cu secs in flood time. It is estimated that when the proposed reservoir is constructed, about one million tons of rice could be produced annually under irrigation. To those who have had any acquaintance at all with the recent distressing famine conditions which India has passed through and is still undergoing, the Lounteous effects which this project will bring about to the country in the future, are obvious. In the region of the proposed reservoir, the river flows for several miles through a hilly tract, hemmed in between flanks of hard, solid rock; but the river bed is mostly sandy. A few bore holes put down in this sandy bed touched rock at a depth of 180 to 200 ft. The river bed is about jo ft above the mean sea level (m.s.l.) and the bedrock was found at —125 to —160 ft m.s.l. The crest of the dam is proposed at +162 ft m.s.l. The proposed dam mould therefore be about 120 to 130 ft above the river bed, and the foundations would have to reach down nearly zoo ft below the bed at the deepest part. A number of alternative sites were proposed for investigation, and it became necessary to quickly ascertain the bedrock topography at these sites. Dr. M. S. Krishnan,* who was consulted in the matter, furnished a detailed account of the geological features of the region and suggested a geophysical investigation which the writer carried out from February to April 1944, employing solely the electrical resistivity methods. The total length of the survey lines for the electrical measurements amounted to 62,600 ft and the number of resistivity determinations was about 2500. Altogether nine alignments for the dam were inten-

Jan 1, 1949

By Magnus Troilius

SINCE the discussion on steel rails in America has forcibly drawn attention to the value of chemical analysis, if not as a necessary stipulation, at least as a guide to control the usual mechanical tests, some doubt has been thrown upon the accuracy of the analytical results obtained by different chemists. To any one having the least acquaintance with chemistry, it is quite clear that if exactly similar results are to be obtained from the same borings of steel, exactly the same methods must be used by the different analysts. Hence the necessity (if complications are to be avoided) of establishing what I may call standard or normal methods, to be used both by the inspectors and by the chemists at the works. Remembering that the application of chemistry to steelrail inspection is yet in its infancy, it is of great importance to possess a perfect acquaintance with the best methods in use. Being myself a grateful pupil of Professor Eggertz, of the School of Mines in Sweden, it occurred to me, two years ago, that I could not do better than start a laboratory of my own, and engage one of his pupils, Mr. Troilius, for the purpose of analyzing the steel borings from mechanically-tested rails, so that I might thus obtain without delay thoroughly accurate determinations. Moreover, in order to carry on the operations in perfect accordance with the methods used at the steel works in England and Germany, where I had to control the manufacture, I deemed it desirable to allow Mr. Troilius to go through a course of training at these works; and I gladly seize this opportunity of expressing my grateful acknowledgments to several works in England and in Germany for affording every facility for such an exchange of information as mas found necessary in arriving at the best analytical methods to be used.

Jan 1, 1882

By M. J. Humenick, K. Garwacka

A laboratory experimental research project was conducted to evaluate the use of chlorine for the oxidative destruction of residual ammonia that may remain in ground water after in-situ uranium solution mining operations. The work tested the idea of injecting high strength calcium hypochlorite solution into the mining zone to convert ammonia to nitrogen gas as a final cleanup process for ammonia removal from the ground water system. This paper details ammonia removal efficiency as a function of chlorine dose, reactant, and product material balances, and how the concept may be used as a final ground water restoration process.

Jan 1, 1985

As bizarre an example of competitive salesmanship to be imagined took place last June in Western Australia. A half dozen world renowned mining groups received a Japanese iron and steel investigatory mission. Geologists, engineers and businessmen, all specialists in iron ore, representing elements of the Japanese government and steelmakers, politely grilled each iron ore group for technical information and plans for property development. At stake were sales contracts with Japan for many millions of tons of iron ore. Since approximately two dozen visitors were involved, it was necessary to divide them into four groups for dispensing information, transportation and accommodations at the remote exploration camps. In a continent noted for its wide open spaces, the hinterland of Western Australia is spectacularly lacking in settlements. The state has better than one third of Australian land and statistically 0.8 persons per sq mile. In reality, however, over 400,000 of the 800,000 population reside in Perth. Under such circumstances, properly receiving and feting these important visitors would seem to be difficult but the competing exploration groups vied ingeniously to outdo each other in hospitality.

Jan 10, 1964

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 Walter R. Hibbard

THE increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform 'compatibly regardless of the single crystal crystallographic strain mechanism, complicates this mechanism so as to increase the metal's resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: "Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of deformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.21 PREVIOUS INVESTIGATIONS Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip were reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elam4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable 34 in: from the boundary. Adcock,6 Yamaguchi,7 Seumel,8 Hirst9 and others have also reported this phenomenon as a qualitative trend. Yet attempts by O'Neill10 and Ljunggren11 to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface the distribution of stresses was so altered

Jan 1, 1948

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By A. H. Daane, R. L. Myklebust

The yttrium-manganese system has been investigated by thermal, metallographic, and X-ray diffraction methods. There are three intermetallic compounds present: YMn2 which melts congruently, YMn4, which undergoes syntectic decomposition, and YMn,, which undergoes peritectic decomposition. The compound YMn4 is ferromagnetic at room temperature with a Curie temperature of 214°C. There are eutectics at 25.2, 60.9, and 82.0 wt pct Mn which melt at 878°, 1100°, and 1075°C, respectively. Crys-tallographic data are given for YMn4, and YMn12 . The terminal solid solubilities are low. In a general program of study of yttrium metal in this laboratory some alloy systems of this metal with elements of the first transition period have been examined. This work was originally instigated by experiences in cladding yttrium with jackets of some protective metals such as Inconel for high-temperature service in air.' In some cases a low-melting phase was observed to form between the Inconel and the yttrium resulting in failure of the samples. In characterizing this reaction, a survey was made of the systems of yttrium with chromium, manganese, iron and nickel,, and it was found that a eutectic was formed between these metals and yttrium on the yttrium-rich side of the system. This present study of the Y-Mn system was carried out to examine in more detail the alloying nature of yttrium, and to correlate trends that have been observed in previous related studies. It was observed by Voge13 that in the systems of lanthanum, cerium, and praseodymium with each of the metals in the first transition series, the tendency to form compounds diminished in the order nickel, cobalt, and iron while no compounds were formed with manganese, chromium, or titanium. Beaudry and Daane4 observed a similar behavior in the systems of yttrium with some members of the first transition series except that the tendency for compound formation was greater. Both the Y-Ti5 and Y-Cra systems consist of simple eutectics, while in the Y-Fe,7 Y-CO, and Y-Ni4 systems, there are four, eight, and nine compounds, respectively. In addition to the above trends, the similar atomic radii and electronegativities of yttrium and thorium invite a comparison between their alloying behaviors with a common element such as manganese. In crys- tallographic studies, Florio et al.' have identified three intermediate phases in this system which are ThMn2, Th6Mn23, and ThMn,,. Gschneidner and Waber10 have examined published information on alloy systems of the rare-earth metals and have correlated this information with current alloying theory. From their study, they predicted that the Y-Mn system would contain one intermetallic compound. On the basis of this prediction, the trend in the alloying behavior of yttrium with the elements of the first transition series and the alloying behavior of thorium with manganese, one might expect from one to three intermetallic compounds to form in the Y-Mn system. A consideration of Hume-Rothery's rules of alloying based on size-factor, electronegativity, and valency suggested a small terminal solubility and possible compound formation. The present study was undertaken to confirm these predictions of low terminal solid solubility and compound formation and to establish the general alloying behavior of yttrium with manganese. EXPERIMENTAL Materials. The manganese used in this investigation was obtained from the Foote Mineral Co. as electrolytic plates of 99.9 pct stated purity; the yttrium metal was prepared in this laboratory. Table I gives the analyses of these materials. For the solubility studies at the yttrium-rich end of the alloy system, distilled yttrium, whose major impurity was 200 ppm Ti, was used. Preparation of Alloys. The alloys were formed by comelting the two metals in an are-melting furnace under an atmosphere of argon. The buttons thus formed were inverted and remelted three to five times to promote homogeneity. Due to the high vapor pressure of manganese, it was assumed that the weight lost during are-melting was all manganese. This assumption was based on the very good agreement observed between calculated compositions and chemical analyses of several alloys. The compositions of the dilute alloys used for solid solu-

Jan 1, 1962