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By W. G. Pfann

A simple method of obtaining multistage batch separations by crystallization was described recently. Known as zone-refining, it comprises passing short molten zones through a long solid charge. This technique can now be used on a continuous basis by means of the zone-void method described in this paper. Feed enters, at an intermediate point, a column down which molten zones travel, and waste and product leave at the ends. Materials move in the column through the agency of voids, which are introduced at the ends and travel toward the feed inlet. The voids and molten zones are moved by external heaters in a simple manner, and the principle of reflux is utilized. ANEW method of obtaining multistage separations by crystallization was described recently.' Named zone-refinina.,-, the method comwrises slowly passing a series of molten zones through a long solid charge. Solute becomes concentrated at one or the other end of the charge, depending on whether it raises or lowers the freezing point of the solvent. The separation increases with the number, P, of zone-passes, approaching a limit as P approaches infinity. Zone-refining has been highly effective in purifying germanium and other substances.2,3 and new applications are steadily increasing. Zone-refining is a batch method and as such it has certain limitations inherent in batch operation. If it could be made continuous, its scope and utility would be greatly broadened. This end has been achieved by the zone-void method described in this paper. In the zone-void method feed is introduced continuously at an intermediate point in a column down which molten zones travel, while impure waste and purified product leave at the ends. Both the flows of feed, waste and product, and also the travels of the zones, are actuated by external moving heaters in a simple manner; and the system utilizes the principle of reflux. The method provides, in the field of crystallization, the counterpart of the continuous fractiona-tion column in the field of distillation. The following will be discussed: apparatus and mode of operation, fundamental nature of the separation, design theory, and practical considerations. The method will be described in terms of a binary solute-solvent system in which the solute is an impurity to be removed and the solvent is the desired product. The distribution coefficient, k, defined as the ratio of solute concentration in the solid freezing out of a molten zone to that in the liquid in the zone, is assumed to be constant and less than one. The process is equally effective for k's greater than one and for ternary or higher order systems. Method and Apparatus The essential features of a continuous zone-refining process are represented in highly generalized form in Fig. 1. A series of molten zones, produced by moving heaters, travels slowly down the column or charge (to the left in Fig. 1). If there were no flows of feed, waste, or product, the process would simply be batch zone-refining, the action of the molten zones being to sweep solute down the column, solvent up the column. For the process to be con- tinuous, with stripping and enriching sections in the column, feed must enter, and waste and product must leave, as indicated. The zone-void process accomplishes both objectives, namely, the indicated movements of zones and the indicated flows of material. Zones are moved by moving heaters, just as in batch zone-refining. Materials are made to flow by creating voids at the waste and product exits and causing these voids to move to the feed inlet. Since there must be a net flow of material from the feed inlet to each of the outlets, the indicated movements of voids are in the desired directions, because movement of a void in a given direction corresponds to flow of material in an opposite direction. In order to produce the desired movements of voids, the column is folded into two vertical sections having the feed inlet in common at their upper ends. Voids are displaced upward by the liquids in the molten zones and their travel is actuated by the motions of the zones. Voids travel with the zones in the enriching section and move continuously. Voids travel opposite to the zones in the stripping section and move intermittently. Creation and travel of voids will now be examined in detail. The enriching section of a column in operation, with its void generator, is shown in Fig. 2. The column section is a vertical tube around which a series of closely fitting, regularly spaced heaters travel slowly upward. Each heater produces a molten region, the temperatures of the heaters and the cooling between heaters being controlled so as to maintain the molten zones approximately constant in size. A void is normally present atop the molten zone in each heater. As the heater rises, it continuously melts solid above it, which drips through the void into the molten zone and continuously freezes out solid below it, of concentration k times that of the liquid in the zone. When a molten zone and void reach the feed inlet, which is kept molten, the void is displaced by an equal volume of feed liquid. Generation of voids of controlled size in the enriching section is shown in Fig. 3. The void generator is a tube of small cross-section, provided with lateral heat-conducting fins which sense the position of the heater. Liquid can escape only when the entire outlet tube is within the heater. If any part of the outlet tube is outside the heater, liquid cannot escape,

Jan 1, 1956

By P. E. Fitzgerald

ACIDIZING, as the terns is used in the petroleum production industry, involves the use of hydrochloric acid in predominantly limestone formations, resulting in the lowering of resistance offered to the flow of oil and gas through the oil-bearing formation, usually with resultant increased production. A number of articles have been written on the chemical treatment of oil and gas wells; a bibliography of these works will appear in Volume 123 of the Institute's TRANSACTIONS (1937), and a few other references are appended to this paper.

Jan 1, 1937

By G. E. Goodspeed

The Cornucopia gold quartz veins form a parallel vein system traversing meta-morphic and granodioritic rocks. Field and petrographic evidence suggests that inetasomatism has played an important role both in the emplacement of the grano-diorite and in the formation of the veins. Structurally the veins appear to be related to the major tectonic features of the Wallowa Mountains and to be narrow shear zones rather than filled fissures. Petrographic studies indicate a complex history of formation starting from initial alteration along fractures or joints followed by recurrent fracturing and a quartz-forming stage, and closing with continued shearing and microbrecciation, which permitted the upward percolation of the later ore-forming solutions. The precipitation of ore minerals from these solutions formed ore shoots. Postmineral effects include the injection of Tertiary basaltic dikes, a shght amount of cross faulting, and some movement along the planes of the veins as well as oxidation. Introduction Cornucopia is in the southeastern part of the rugged Wallowa Mountains of northeastern Oregon. It was founded over 50 years ago following the discovery of its system of gold quartz veins. The major veins are roughly parallel and dip into the western side of Pine Valley, which drains the southern slope of the range. Previous operations had cut the upper portion of four major veins with two tunnels over 1000 ft. apart, when the present operating company drove a third tunnel, called the Coulter, at the level of the valley over 1000 ft. lower to intersect the most easterly major vein at over 6200 ft. from the portal. General Geology of District The oldest rocks in the vicinity are metamorphosed sediments and volcanics. These, for the most part, are presumably Mesozoic in age, although some black argillites outcropping along East Pine Creek are considered to be Permian.l,2 These rocks have been deformed and metamorphosed in general to hornfels at the close of the Jurassic. The series was then invaded by a granodiorite batholith, the origin of which is

Jan 1, 1941

By G. E. Goodspeed

The Cornucopia gold quartz veins form a parallel vein system traversing meta-morphic and granodioritic rocks. Field and petrographic evidence suggests that inetasomatism has played an important role both in the emplacement of the grano-diorite and in the formation of the veins. Structurally the veins appear to be related to the major tectonic features of the Wallowa Mountains and to be narrow shear zones rather than filled fissures. Petrographic studies indicate a complex history of formation starting from initial alteration along fractures or joints followed by recurrent fracturing and a quartz-forming stage, and closing with continued shearing and microbrecciation, which permitted the upward percolation of the later ore-forming solutions. The precipitation of ore minerals from these solutions formed ore shoots. Postmineral effects include the injection of Tertiary basaltic dikes, a shght amount of cross faulting, and some movement along the planes of the veins as well as oxidation. Introduction Cornucopia is in the southeastern part of the rugged Wallowa Mountains of northeastern Oregon. It was founded over 50 years ago following the discovery of its system of gold quartz veins. The major veins are roughly parallel and dip into the western side of Pine Valley, which drains the southern slope of the range. Previous operations had cut the upper portion of four major veins with two tunnels over 1000 ft. apart, when the present operating company drove a third tunnel, called the Coulter, at the level of the valley over 1000 ft. lower to intersect the most easterly major vein at over 6200 ft. from the portal. General Geology of District The oldest rocks in the vicinity are metamorphosed sediments and volcanics. These, for the most part, are presumably Mesozoic in age, although some black argillites outcropping along East Pine Creek are considered to be Permian.l,2 These rocks have been deformed and metamorphosed in general to hornfels at the close of the Jurassic. The series was then invaded by a granodiorite batholith, the origin of which is

Jan 1, 1941

By PHILIP N. MOORE

THE development of the power of the Tennessee River at Muscle Shoals has become a matter of political interest as well as engineering possibility. The controversy over it has been so active that the facts have been obscured, the possibilities exaggerated. Although the members of the American Institute of Mining & Metallurgical Engineers are not generally specialists in hydroelectric development, those who visited Muscle Shoals in October, following the Birmingham meeting of the Institute, were interested, and many of them surprised to learn the actual conditions. These have long been familiar to those who have studied the matter through the reports of the U. S. Engineers on the subject. The approved plan contemplates three dams-No. 1, a low dam close to the City of Florence, planned in the interests of navigation, since the construction of the other dams has rendered impossible the use of the river without it. No. 2-named the Wilson Dam is now under construction. Concerning it political argumentation has waged. No. 3 Dam-much smaller, is planned to be erected several miles above No. 2.

Jan 1, 1925

By AUDLEY H. STOW

I. INTRODUCTION. THE general drift of the discussion as to the relative merits of pressure- and exhaust-fans has resulted, if we may judge from the prevailing practice, largely in favor of the latter. The subject has been hitherto treated, however, with special reference to highly gaseous mines, the effect of the form of ventilation upon dust-explosions having been too little considered. Even in mines containing practically no gas, dust-explosions may occur; and if, as I believe, pressure-fans are to be preferred for their effect upon dust, it may be worth while to reopen the debate, and to challenge the advisability of exhaust-ventilation under certain conditions. There are several forms of colliery-ventilation, which may be described as follows: Plain or simple pressure-ventilation, in which the fan acts as a pressure-fan, and the movement of coal is unobstructed at the surface by doors or equivalent devices in drifts or shafts, the traveling and haulage thus being in the return-current. Plain exhaust-ventilation, in which the fan acts as an exhaust-fan, the movement of coal being likewise unobstructed at the surface, and the traveling and haulage being in the intake. Obstructed pressure-ventilation, in which the movement of coal is obstructed at the surface, in order that the traveling and haulage may be in the intake. Obstructed exhaust-ventilation, in which the movement of coal is obstructed at the surface, in order that the traveling and haulage may be in the return. The apparent advantages in running a fan "pressure" during working-hours, and " exhaust" between shifts, seem to justify the recognition of this combination as a standard form of ven-

Feb 1, 1909

By Joseph Daniels

IN connection with a study of the feasibility of establishing a blast-furnace industry in the Puget Sound region of Washington, possible sources of ore supplies along the Pacific rim were investigated. Many of the South American countries are known to contain important resources of iron, particularly Brazil and Chile. This latter country, because of its position on the west coast and the easy accessibility of its de- posits, appeared to be a logical place to consider as a potential supply for the Pacific Northwest. Accordingly, a brief field study was made of the deposits in September, 1924. Attention was confined to a limited number of properties on the west coast in the provinces of Antofagasta, Atacama, and Coquimbo. Passing consideration was given to the question of coal resources, and a short visit was made to a blast-funace plant at Corral in southern Chile which had been operated for a limited period as a producer of pig iron. In the following paper, a brief outline is given of the general observations made and of the salient facts rioted in the time available for the general study.

Jan 1, 1926

By B. E. Warren

Jan 1, 1965

By Alan M. Bateman

POSSIBLE postwar trends of the more important world minerals will be determined in part by their present world position and by the acts and forces that have operated during the war period, so it is desirable first to review briefly what has been happening in the foreign field of metals and minerals. When we first entered this war we of the mineral profession were all acutely conscious of our lack of strategic minerals and other materials, which had to be imported in great quantities-minerals such as manganese, chrome, tin, mercury, nickel, and antimony. But we realized also that we had to acquire vast quantities of those minerals of which we had thought we were bountifully supplied. Our assumed domestic abundances turned out to be woefully deficient, and demands also arose for new minerals never before produced in large quantities. Some threescore minerals entered the strategic list of our imports. Ores from new sources had to be sought, developed, and transported. Tonnages in the millions of such bulk materials as zinc, lead, copper, chrome, and manganese flowed to feed our war efforts. Sparsely distributed minerals such as tin, mercury, antimony, tungsten, cobalt, mica, and corundum had to be lured from their rock lairs in greatly increased quantities to feed the hungry maw of war industry, and the rare minerals such as tantalite, columbite, beryl, and quartz crystals had to be developed and procured in quantities never before dreamed of. New uses such as radio and radar created demands for many minerals formerly thought of only as adornments of museum collections and not as pressing industrial minerals. Such minerals were never before mined in quantity.

Jan 1, 1945

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.' It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12'13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By Robert Linton

AT its meeting on May 21, the Board of Directors approved the recommendations submitted by President Lovejoy and named a nominating committee for the year that is especially well distributed as to major technical interest and as to geography. As may be seen from the list published herewith, two come from the East, two from the Midwest, and three from the far West. Mr. Linton, the chairman, has been a valued member of the Institute for 36 years. A memorandum drawn up by Paul D. Merica, representing the A.I.M.E., and W. R. Barclay, representing The Institute of Metals of Great Britain, setting forth a reciprocal plan for special memberships in each Institute for members of the other, was discussed. Both societies already have formally approved the plan in principle and Dr. Merica was clothed with full authority to agree on a few small details that have not been settled, and conclude the arrangement in behalf of the Institute.

Jan 1, 1936

By O. C. Wheeler

In order that the series of reports on oil and gas in Colombia may be complete, the report for the year 1941, which was not available for Volume 160 of the TRANSACTIONS, is given here. The report for 1945 begins on page 4o6.

Jan 1, 1946

By AIME AIME

A REQUEST for information as to the details of activities of the Engineering Council was made by the Joint Conference Committee for the benefit of the new American Engineering Council. , This request was complied with, and the scheduled reply so succinctly sets forth the activities of the old Council as well as the scope of possible activities of ,the new Council, about whose efforts there has been much discussion, .that it' is given herewith in full, except the 'budget which is summarized.

Jan 1, 1920

Jan 1, 1920

By Henry Sturgis Drinker, Rossiter W. Raymond

Jan 1, 1914

By H. M. Chance

Jan 1, 1886

By Maurice Magee

The Ducktown ore deposits have been known, explored, and mined for 120 years. Eight massive sulfide ore bodies occur in highly folded and metamorphosed graywacke, graywacke conglomerate, mica schist, chloritegarnet schist, and staurolite schist of Precambrian age. The ore deposits are tabular bodies that have been extensively folded, generally conform to the enclosing rocks, but show local complex differences. The ore deposits, ranging in size from 250,000 tons to over 20 million tons, are composed principally of the minerals pyrrhotite, pyrite, chalcopyrite, sphalerite, and magnetite. Gangue minerals are quartz, calcite, actinolite, tremolite, hornblende, garnet, and masses of schistose wall- rock. Three fault systems are present that have influenced ore control and ore body configuration. Hydrothermal effects are evident in wall-rock alteration. Evidence of retrograde metamorphism is extensive in the wall and ore associated rock. Preliminary isotopic age dates have indicated four possible metamorphic events during the Paleozoic Era. Ore genesis is considered to be hydrothermal replacement of receptive beds, predominantly highly calcareous zones, quartzitic zones, and brecciated shear zones. Ore deposition is thought to have occurred during the Devonian Period, with later mobilization and recrystallization of the ore and gangue during Middle and Late Paleozoic times.

Jan 1, 1968

By E. C. Wright

FOR many years the cost of making pig iron and steel in the Birmingham district has been about the lowest in the United States. The close proximity of the important raw materials such as coal, iron ore, limestone, and the large available scrap supply made it possible to assemble all of the important ingredients necessary for steel- making with only nominal costs for transportation. Both iron ore and coal were being mined in this district at one time for about $1 per ton from underground operations. At that time mining wages were low everywhere and the labor rate in the South was considerably below that of other mining districts. This situation persisted until the emergence of labor unions as an economic and political force, emigation of southern labor to northern plants, and continued growth of industry in the South in the years following the depression of 1932. Since that time union organizing of miners and steel workers throughout the nation has increased labor costs in mining and steelmaking. This influence has been felt particularly in underground mining operations since the proportion of labor cost to total cost is still high. The previous advantage in basic labor rate in the South has been almost entirely eliminated by the equalization of labor rates in basic industries by national unions. Since 1945 these influences have been especially noticeable in increasing the cost of mining coal and iron ore in the South. The northern steel districts are still being largely supplied with iron ore from the Minnesota open-pit mines and the cost of this ore has not increased nearly as much as the cost of ore obtained from underground mines in Birmingham. A similar situation exists in coal mining; the thinner seams in Alabama are not so amenable to mechanization as the northern mines and, as a result, the output per man-day in southern mines is only about three tons of coal as compared to five or six tons per man-day in the large captive mines of West Vir-

Jan 1, 1950

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations'j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.' Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.' Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini's work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969