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By A. M. Abouzeid, S. Chander, D. W. Fuerstenau

Today numerous ores contain valuable minerals in finely disseminated form; and although the recovery of these fine mineral particles is generally exceedingly difficult, diminishing raw material resources necessitates the recovery of such mineral values. In many systems, the efficiency of recovering fine particles is still extremely low and often fine particles must be discarded as slimes. However, in recent years, various advances have taken place in the recovery of mineral particles in the very fine size range. In this paper, the background and performance of a number of processes for fine particle processing and separation are reviewed and discussed, particularly from the point of view of how fine particle recovery might be improved.

Jan 1, 1979

By R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13. per cent, of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 258, Special 178 and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings.

Jan 1, 1927

By E. P. Abrahamson, S. L. Lopata

A general relalionship between the amount of glide shear (due to slip) and the macroscopic shape change has been developed. Since the deformation can be large, finite strain analysis is employed. In this treatnzent, the shape change is expressed by a deforlnation gradient matrix, F - [axi/aXj/ where X and x refer lo the initial and final positions of a particle. This matrix is readily evaluated in termas of the amounl of glide shear, a , and the direction cosines of the slip-plane normal and the slip direction for a single active slip systena. In the case of deforma tion from slip on several systems, the product F(a) of the several deformation gradient matrices is first calculated. Then, by assuming that the final configuration is reached by a long series of small shears of magnitude a, occurring more or less alternately in the several slip sys- IN problems of crystal plasticity, it is often necessary to relate the amount of glide in the operating slip systems to the macroscopic strain components. This relationship is relatively simple when only small strains are considered. In this case the separate strain contributions from several slip systems are additive. Such a procedure is incorrect in the case of large plastic deformation. To the authors' knowledge, no general treatment of the latter problem has appeared in the literature. In specific instances, Mark, Polanyi, and schmid3 have derived the relationship between glide and axial elongation during tensile pulling of a single crystal when only one slip system is active. A similar relationship for duplex slip was worked out by v. Göler and Sachs.4 Taylor and Elam1 have also studied in detail problems of large plastic deformation. Due to uncertainties as to the slip systems at the time, ! terns, the final deformation gradient matrix can be obtained. Mathematically, the problem is reduced to finding the limit of F(aN as N — m while a — 0 in such a way that the Product Na = a finite conslant designatzng the accumulated amount of shear. It turns out that this limit is simply eafF1, where F, is the matrix whose elements are the coefficients of a in the F(a) twatrzx. Application is made of the present treatment to a fcc crystal of Permalloy compressed on the (110) plane and contrained to elongate in the [112] directzon. In addition, it is shown that one rnay readily obtain from the general analyszs the well-known formulas relating elongation, amount of glide shear, and amount of lattice rotation for crystals deforming by single and double slip under tension. however, they were mainly concerned with proving that slip occurs on {111}(110) systems in fcc metals. The present general treatment arose out of recent investigations of magnetic anisotropy in cold-worked Fe-Ni alloys6 as well as some related problems in strength anisotropy of single crystals.' Detailed application of the general analysis will be provided in the case of a Permalloy single crystal compressed on the (110) plane and constrained to elongate only in the [112] direction. It will be seen that, as expected, the small strain approximation leads to significant errors after moderate straining. It will also be shown that the present general treatment yields the formulas of Mark et al. and of v. Goler and Sachs in those specific cases. GENERAL CONSIDERATIONS Consider a homogeneous deformation in which a material point initially at moves to (xl,xz,x3), both positions being referred to the same set of Cartesian axes. Such a deformation can be

Jan 1, 1967

By Robert Richards

Introduction. WALTER RENTON INGALLS recently gave a very interesting talk before the student mining society of the Massachusetts Institute of Technology. In it he showed the present status of mining as he sees it. In the talk he explained that, while discoveries of great mining districts are still possible, they are being made less and less often; that the great mining companies, although there are large numbers of mines offered for sale, are finding it less and less possible to find new mines that are up to the standard of richness that they wish for purchase. The natural conclusion is that better, cheaper, and more efficient methods of mining, concentrating, and smelting are needed if the lower-grade mines are to be worked at a profit. This is true also if the high-grade mines are to yield their greatest profit. This paper deals only with the concentrating or ore-dressing problem, and gives some thoughts which point towards greater profit. In a paper on The Development of Hindered-Settling Apparatus the writer showed that there were two main lines of work that would lead to greater saving, lower tailing assay, and, therefore, greater profit. The first is the recrushing of middling or tailing products for the saving of the contained values. This is well understood and largely carried out in existing mills. The second is the saving of fine free mineral at the first opportunity. This is a matter less well understood in the mills, and to dwell upon this the present paper is written.

Jan 9, 1913

By J. K. Kerver, J. S. Osoba, J. G. Richardson, J. A. Hafford

A detailed study of a number of methods of relative permea-abilitv measurement has been made in a search for the tech-niqrle most suited to routine analysis of cores taken from reservoir rock. It has been found from tests run on the same samples of core material by a number of techniques that the Penn State, Hassler, Hafford, and dispersed feed techniques all yield results which are felt to be reliable. Conditions under which the faster single core dynamic technique may be used are described. Further work on the calculation of relative permeabilities to oil from data obtained by the gas drive method is needed before this latter rapid method can be utilized. Correlations between theoretical studies and experimental results have been obtained in studies of the boundary effect. pressure distribution in two-phase flow, and gas expansion effects. Previous conclusions that the effects of the outflow boundary could be made negligibly small have been substantiated. Results of experimentally determined oil and gas pressure distributions along a core sample during flow are presented. Further studies of the effects of rate of flow in the measurement of relative permeability-saturation relations have shown that results are independent of the rate of flow as long as the flow rate is below the point where inertial effects commence. An analysis of the effects of a severalfold expansion of gas along the flow path indicates that while saturation gradients are induced in the test sample, the errors caused by this phenomenon in relative permeability measurements are small. INTRODUCTION Many pages of literature have been devoted to pointing out the need for relative permeability-saturation relations in reservoir engineering. One of the most attractive ways of obtaining this information is by the analysis of samples of core material taken from the formation in question, and again literature has described man); methods for obtaining these data. It is the purpose of this paper to present the work that has been done in the study of some of these published methods together with some other methods that have been recently developed in this laboratory. Also, a study of some of the factors that influence the laburatory determination of relative permeability-saturation relations is presented. FACTORS WHICH AFFECT LABORATORY STUDY OF FLUID FLOW THROUGH RESERVOIR ROCK To determine relative permeability-saturation relations of samples of reservoir rock in the laboratory, it is important to know what factors affect these measurements in order that the magnitude of these effects can be ascertained and steps then can be taken to eliminate or, in some cases, to minimize them. The factors that have been investigated are the boundary effect, the effect of gas expansion. and the rate effect. Boundary Effect In laboratory experiments in which two immiscible fluids are flowed through a porous medium, there exists a discontinuity of capillary properties at the outflow face. This discontinuity exists became the fluids pass from a region of finite capillary pressure in the sample to a region of zero capillary pressure in an open receiving vessel. The capillary forces existing in the core caupe the rock to tend to retain

Jan 1, 1952

By F. R. Morral, E. P. Miller

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By E. P. Miller, F. R. Morral

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By ROBERT E. HARDWICKE

THE QUESTION of whether the production of oil should be limited to market demand has been constantly discussed during the last two years. Oil men, legislatures and courts have reached highly conflicting conclusions. Opponents of limitation to market demand assert that it is a scheme of the big purchasing companies to fix prices and to create a monopoly. Proponents, on the other hand, declare that such a limitation is necessary to prevent physical waste and that the effect on prices is merely incidental. A brief review of market demand legislation will disclose the confusion existing. The laws of Oklahoma,' prohibiting waste of oil and gas, specifically' authorize limitation to market demand as a method of preventink such waste. These laws and the proration orders based thereon have been upheld by the Supreme Court of Oklahoma, by several three-judge Federal District Courts, and by the Supreme Court of the United States.' Kansas has a similar law3 but no case has been found which discusses its validity. About a year ago the California Legislature passed a comprehensive conservation act, generally known as the Sharkey Bill giving authority to restrict production to an amount representing current requirements for use, taking into consideration oil and products in storage. This may be considered as equivalent to limitation to market demand. The Act was defeated upon referendum vote after a hard fought campaign in which it was charged that the Act would result in destruction of the independent operators.

Jan 1, 1932

AN excerpt from the Odessa Isvestia Vechernia, dated April 24, 1927, and translated by P. Routzitzky, summarizes a report by Professor Preobragensky ad-dressed to the Russian Government. Professor Preo-bragensky writes in regard to newly discovered potash deposits in eastern European Russia. Near Solikamsk in the Perm district, about 100 miles east of the Ural mountains and on the Kama river, large deposits have been located and the belt has been traced southward about 25 miles. Subsequently the search for potash salts has been transferred to the Berezovsky district, near Nikolsk, on the Kosva river, about 70 miles north-east-of the city of Perm. Toward the end of March, 1927, at a depth of 800 ft., drilling at the Levensk salt works revealed potash salts in, definite strata. The bed has a thickness which extends from a depth of- 245 to 307 meters (latest data in middle of April, 1927) and has not been bottomed yet. Professor Preobragensky goes on to say that these operations have definitely, developed very large de-posits, the limits of which are still unknown. There is at least an implication that the reserves far exceed those of Stassfurt, Germany. For European use they are, of course, much less accessible, for by through rail they lie 1200 miles east of Petrograd. Further, no particulars are given as to the potash content. It is to be supposed that the salt occurs in the Permian beds that extend north and south along the west flank of the Ural mountains, as the localities mentioned .all lie within the area so mapped on the new geologic map of Russia issued by the Scientific and Technical Di-vision of the All-Russian Council of Soviets in 1922. It is interesting to note that these salt beds are of the same geologic age as those of 'the Stassfurt region and of the west Texas-New Mexico district, in which the U. S. Bureau of Mines is at present drilling.

Jan 7, 1927

By Robert Williams

A description is given of a double heat treatment of 60-40 brass. Photomicrographs are included to show the changes that take place in the microstructure on reheating the water-quenched specimens. A wide variation in the mechanical properties may be obtained by the described heat-treatment method. ON SEVERAL occasions, when 60-40 brass is first obtained in the beta condition by quenching at about 825° C. and is then reheated, the writers have noticed that recrystallization will take place in the form of twin crystals at the grain boundaries of the original beta crystals. It was, therefore, thought that interesting results would be obtained if this twinning process was studied further, especially as to the temperature at which it first occurs. The material used in the investigation was a bar of extruded muntz metal, 1/2 in. in diameter, and of the following composition: Copper, 60.21 per cent.; zinc, 39.73 per cent.; lead, trace; iron, trace; tin, nil. Specimens I in. in length were sawed from this bar and a hole was drilled into the side of each specimen until it reached the center, and the tip of a platinum-platinum rhodium thermocouple was inserted. A small Hoskins' resistance-type electric furnace was used for heating the specimens. The specimens were first heated at 840°C. for 2 hr. and then quenched in cold water, in order to get the material entirely in the beta state. In every case, in the reheating process, the furnace was brought to the desired temperature before the specimen was introduced. The time occupied in preheating was from 20 to 30 min. By sawing back 1/4 in. on each side of the hole, two parts were obtained from each specimen

Jan 3, 1924

By George C. Bateman

WE in Canada want to see industry get back to a normal economic basis as soon as possible but wartime controls cannot be dispensed with immediately the war is over. Perhaps never again will we be entirely free from some of the types of controls such as those set up during the war. Certainly the taking over and disposal of surplus materials contemplates the continuation of some form of control for many years to come. However, to the extent that it is possible, the Allied nations are exponents of free enterprise.

Jan 1, 1944

By H. Conrad Meyer

The wizardry of nucleonics has added new and greater dimensions to the almost inseparable "twins"-zirconium and hafnium. So close is their relationship that neither element is found free of the other in any presently known mineral. Although zirconium in the form of its oxide was discovered in 1789 by Klaproth, the metal in an impure, nonductile form was not isolated until 1824 by Berzelius. About 100 years later -1925-van Arkel and deBoer developed and patented a technique for the deposition in vacuo of crystalline, coherent, highly ductile metal of extreme purity on an electrically heated filament through the dissociation of gaseous zirconium tetraiodide. Within the past five years both zirconium and hafnium have been dramatized by the press and in popular science magazines. This has led to the false assumption that practically all of the world consumption of zirconium ores is used in the production of the metals. Recent statistics on the subject show that not over 15 pct of the zirconium ore consumed in 1958 went to ferrosilicon zirconium and zirconium metal. The rest was consumed in refractories, foundry sand and facings and ceramics. The importance of zirconium as a component in compact, relatively lightweight nuclear energy units, such as those now used in the submarine Nautilus,6 is well established. A rival of zirconium metal as a casing for atomic fuels is a newly developed ceramic body. It is claimed to be cheaper than zirconium-to withstand higher temperatures-and to be more resistant to corrosion. Whether such ceramic casings have the required low thermal neutron absorption cross section, high strength and easy formability of zirconium is yet to be demonstrated. Hafnium, because of its low order of abundance and its close chemical relationship to zirconium, was not definitely recognized as a new element until around 1923, despite prior claims. A study of the X-ray spectra of zirconium led to its identification. The circumstances leading to the discovery of hafnium were much less fortuitous than those surrounding zirconium. The more precise tools of arc and X-ray spectrometry lent themselves admirably to the search for elements to fill certain gaps in the periodic table. [ ] Pure, ductile hafnium-a metal similar in appearance to stainless steel-has a specific gravity of 13.3 (zirconium 6.52) and a melting point of 2,200°C. In other respects it closely resembles zirconium except in one important respect which gives it a preeminent position in nuclear energy development, namely, a high thermal-neutron absorption cross section. This explains the necessity of hafnium-free zirconium in atomic piles. The ability of hafnium to capture thermal neutrons makes it an excellent "moderator" of "governor" when used as control rods in nuclear reactors (Table 1).

Jan 1, 1960

The 128th meeting of the American Institute of Mining and Metallurgical Engineers constituted a two weeks trip through the Great Northland of Ontario and Quebec and was a most memorable occasion. The last visit of the Institute to Canada was made in 1907 when the mines, which now have brought world wide fame to some of the camps, were not yet dis-covered. The party reached its greatest numbers at Porcupine where 167 visitors and nearly one hundred local members participated. Five members of the party from the States were on the previous trip in 1907. They were Mr. and Mrs. L. D. Huntoon, John Stevenson and son and E. F. Eurich. The Minister of Mines for the Province of Ontario attached his private car to the "Mining Engineers' Special" and made the complete trip through Ontario. This was a happy incident in many ways and gave the visitors an opportunity to discover a spirit of mutual accord between the Minister and mining industry that might well be emulated elsewhere. Two compartment cars and one standard Pullman with the Institute members from New York and the metropolitan district were attached special to the 6.15 p.m. Lehigh Valley train from New York, Sunday, Aug. 19, en route to Toronto, where was held the first session of the Institute's 128th Meeting.

Jan 9, 1923

By D. M. James, J. C. Martin

The results are presented of a study of the application of analytical methods to the solution of two-phase flow into single wells. Approximate analytical expressions for the pressure distribution in two-phase flow are found ;;; a number of conditions. The results obtained from the analytical solutions me found to be in good agreement with results obtained by finite difference techniques using a high speed digital computer. Mathematical solutions for four sets of boundary conditions are presented. All of these solutions are composed of a short-term transient plus a steady or quasi-steady state. The rates of decay of the short-lived transients are analyzed. It is found that the durations of the short-term transients may be characterized by a parameter defined as the time constant which can be determined from simple relations. It is shown also that if the outer radius is much greater than the radius of the well. the short term transients decay at rates which are proportional to the square of the exterior radius, and the rates of decay are only slightly dependent upon the radius ratio. Numerical solutions based on finite difference techniques are presented for a number of conditions. The numerical solutions are in good agreement with the predictions based on the theoretical analysis for small and moderate drawdowns. Examples involving large drawdowns indicate that the nonlinearities in the equations of flow do not appreciably alter the longevity of the short-term transients. In all cases the time required for the short-tern transients to disappear is predicted satisfactorily. INTRODUCTION The mechanism by which oil and gas flow into a single well is of vital interest to the petroleum industry. The fundamental equations of two-phase flow which describe this mechanism are nonlinear partial differential equations. Numerical solutions of these equations describing pressure transients have been obtained with the aid of electronic computers. Although solutions obtained in this manner take into account a large number of effects, the reduction of this information to useful generalities is difficult. One method of obtaining generalities is the use of linearized approximations of the nonlinear equations. Since it is possible to obtain explicit solutions of the linearized equation, general properties of the role of pressure in the flow mechanism may be ascertained. Results obtained from this approach are limited to some extent by the linearizing assumptions. The severity of these limitations may be evaluated by comparing solutions of the linear equation with numerical solutions of the more exact nonlinear equations of two-phase flow. In the past considerable amount of work has been devoted to studying pressure build-up using the single-phase flow theory. Unfortunate1y, most prep sure build-up tests involve multiphase flow. A small amount of work has been done studying pressure build-up where the flow is two-phase. The encouraging results of these studies suggest that useful results may be found from additional studies of not only pressure build-up, but also the rapid transients associated with placing a well on production. This paper presents the basic theory of the pressure transients associated with placing a well on production and with closing it in. The paper is concerned chiefly with two-phase compressible flow; however, the results also apply to single-phase flow. The results are based on analytical solutions of the flow equations, and they are verified by numerical solutions using finite difference techniques. Much of the previous work on compressible flow into wells has been confined to single-phase flow. Some work has been done on compressible two-phase steady state flow, and solutions of the equations of flow have been found by finite difference techniques using high-speed computers. Muskat1 presents some rather general solutions to the equations of single-phase compressible flow into wells. Much work has been done on pressure build-up in wells (see, for example, Refs. 2-6). Almost all of the work on pressure build-up concerns single-phase flow with the exception of Ref. 5 and part of Ref. 2. Some work has been done on pressure fall-off in injection wells.718 Muskat9 presents the solution of the equations for radial steady state two-phase compressible flow. Handyl0 extends Muskat's solution to obtain

By William F. Boericke

THERE was a time when the selection of fire brick was .left to the judgment of the head bricklayer of the plant, whose choice was not unaffected by a box of Christmas cigars from a friendly salesman. But the days are past when it was generally believed, with complacent philosophy, that bricks were bricks without much distinction, and should be bought on a price basis alone. Gone, too, is the belief that in certain types of industrial work the eventual failure of refractories was assured. Modern metallurgical practice, with its trend toward handling larger tonnages at higher temperatures, demands the use of refractories that cannot be supplied by random guess. The logical development is to inquire into the properties of the brick to be purchased, and this resolves itself into the use of specifications. In 1925, the General Refractories Co., with the active support and hearty cooperation of some of its larger customers, established a laboratory, at its Baltimore plant, for testing and research in refractories. This was the outgrowth of a growing appreciation of the value of research in the refractory field. Since then the work has become more involved' and the aims more ambitious, so that the present laboratory now employs a staff of 11 men working, under the direction of trained refractory technologists, on problems of research as well as the routine control of manufacture. It is believed s that `this type of laboratory is a comparative novelty among refractory manufacturing plants. It handles the testing and research work for all the 15 plants of the organization. Being at one of the works has the advantage of making it possible to carry on large scale plant tests on new products after the preliminary laboratory tests have been successfully completed.

Jan 1, 1929

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By L. C. Morganroth

Magnesites are of two general classes - massive and crystalline.

Jan 1, 1915

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952