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By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By E. Buehler, E. Berry

HE magnetic properties of dilute palladium alloys are of fundamental interest.''' Neutron diffraction studies3 have indicated that a better understanding of the behavior of these alloys could be realized with the availability of high-purity single crystals of palladium. Crucible melts of 99.999 pct pure palladium were found inadequate for such research. In a successful effort to fill this need, floating zone refining of palladium was undertaken. In this note the results of the initial experiments are reported. Zoning was accomplished in an argon atmosphere using 450 kc rf generator for an energy source. Samples 5 to 6 mm in diam were suspended in a gastight quartz envelope which could be moved vertically through the rf coil. A nominal upward traverse rate of 1.5 mm per min was maintained during a pass. Close coupling was found to be essential for stable retention of the liquid in the zone. Single crystals averaging 3.5 cm in length were obtained. Laue photography showed them to be continuous single crystals without gross imperfections. Several criteria were used for evaluation of the purity of the zoned material: magnetic behavior, low-temperature specific heat and residual resistivity ratios. Table I shows the residual resistance ratios obtained for two samples, one subjected to a single pass, the other zoned four times. It is appilrent that palladium can be zone refined with the electrically active impurities being transported toward the tail end. A decrease in susceptibility for zone-melted specimens over any previously measured material from 1.5" to 80'~ has been obserted by H. J. Williams and R. C. Sherwood4 substantiating the residual resistance data. The specific heat measurements are currently being made3 and will be published at some later date. Discussions with J. H. Wernick and S. C. Abrahams are acknowledged. We also wish to thank G. F. Brennert for the residual resistance measure ments.

Jan 1, 1962

By R. E. Whippo, B. L. Murowchick

The commercially exploited sedimentary apatites exhibit a number of variable lattice substitutions which affect their chemical composition. Carbonate is a major diluent of phosphorus values in sedimentary apatites. Substantial amounts of water as hydroxyl, hydronium, and tetrahedral hydroxyl ions substitute for fluorine and oxygen, calcium, and phosphate, respectively. Calcium is also replaced by several other divalent and monovalent cations. The structural formula demonstrates the substitutions in the lattice of the sedimentary apatites studied in view of the crystal-chemical relationships which have been postulated for the isomorphous apatite series. The lattice constant a. varies from 9.29 to 9.40 A for the apatites studied. Quantitative relationships between this constant and lattice substitution are complicated by the interaction of multiple substitutions whose influence is non-additive. The mineral apatite, the principal raw material source of phosphorus for agricultural and industrial applications, offers a wide area for investigation. Considerable research effort has been expended in the study of apatite crystal-chemistry by medical, biological, and earth scientists. Few of these studies deal directly with the sedimentary apatites from the major occurrences which are widely exploited for commercial uses. It is the purpose here to present chemical analyses of several sedimentary apatites and discuss their chemical composition in relation to the structural and crystalchemical principles which have been postulated for the apatite isomorphous series. THE STRUCTURE OF FLUORAPATITE The atomic structure of fluorapatite was described, independently, by Ngray-Szabd and Mehmel in 1930 and has been accepted as presented, with only minor changes,4 since that time. The hexaogonal unit cell with dimensions of a = 9.37 0.01 A and c = 6.88 0.01 A contains two molecules of the composition "There are six (PO4) groups in the cell, four calcium ions on the trigonal axes, surrounded prismati-cally by six oxygen ions and six calcium ions surrounded by an irregular polyhedron of a fluorine and five oxygens. Fluorines are at the comers of the reflexion planes, touching three calcium ions each".l7

Jan 1, 1968

By E. M. Boatman, S. J. Pirson, R. L. Nettle

More than a decade ago some theoretically derived relationships were proposed that permitted the prediction of the relative ability of reservoir fluids (oil, gas, water) to flow simultaneously within the porous structure of rocks. While many successful predictions of fluid-flow ratios from wells have been made from electric logs, the theoretical deductions have not been subjected to laboratory verifications. For the relative permeability to liquid and gas, simultaneous flow of water and air was used, employing the familiar external-gas-drive technique. While in the process or water desaturation, the resistivities of the test cores (Woodbine sand) were measured. Their permeabilities varied from 10 to 280 md. The laboratory results indicated the need for changing the values of exponents in the theoretically derived formulas, whereas the form of the functions of resistivities and saturations remained as derived by theory. For the relative permeability to oil and water, the three-core dynamic technique was used on six cores. In this case it was found that the formulas were valid with but slight modification as derived by theory, to a sufficient degree of accuracy for engineering use and for well productivity prediction from electric logs. INTRODUCTION Conventional quantitative well log interpretation generally stops after reasonable values for formation porosities and water saturations have been established. Yet such in formation is insufficient to predict either the outcome or the desirability of well tests and completion, let alone the economic aspect of producing oil- and gas-bearing sections which might have been established by conventional log analysis. To give an engineering answer to such questions, it is necessary to predict the expected fluid flow ratios, the productivity index and the ultimate recovery from potentially productive wells. This problem requires in part for its solution a determination of the relative permeability characteristics of the potentially producing formations, both to oil (or water) and gas, and to oil and water.

Jan 1, 1965

By C. H. Hitchcock

The puiblication by the Institute of a small geological map of the United States calls for an explanation of its peculiarities. The title intimates that it is intended "to illustrate the schemes of coloration and nomenclature recommended by the International Geological Congress." By way of further explanation it is said to be "based, by permission of the Director of the United States Geological Survey, upon the map published in his Fifth Annual Report, the portions not colored in that map being here supplied from other sources." The map referred to was prepared by W. J. McGee, and in the text of the report containing it he has given a list of the authorities employed in the compilation. The scheme of coloration used for the map was the one proposed by the Director, in the Seeond Annual Report, for the publications of the United States Geological Survey, which differed materially from those employed by the older American geologists. Because of the increasing diversity in the particular colors employed to represent rocks by geologists in different countries, and of the existence of very dissimilar schemes of nomenclature, it seemed best to the American Association for the Advancement of Science, at its Buffalo meeting in 1876, to appoint an international committee of geologists, who should consult together, and, if feasible, to call an International Congress to discuss these subjects. The proposition met with favor, and the meeting was called. The first session was held at Paris, in 1878, when geologists were present from twenty different countries. Once organized, the Congress has perpetuated itself, enacting regulations for its conduct, choosing the French language for its medium of communication, and arranging for the compilation of a geological map of Europe upon which the perfected schemes of coloration and nomenclature will be delineated. The American Association maintains a standing committee to represent it at the international sessions, and to report their proceedings. Sixteen countries were represented at the second Congress, at Bologna;

Jan 1, 1887

By R. D. Barer, M. B. Bever

Age hardening alloys are quenched from the solution treatment to room temperature in order to retain a supersaturated solid solution. Some alloys age "naturally" in this condition but in most alloys aging is induced "artificially" by heating to intermediate temperatures. Cold working of the supersaturated solid solution accelerates the aging process and quenching strains have the same effect. The investigation reported here is a study of the progress of aging in specimens quenched directly from the solution treatment to various aging temperatures. This procedure reduces the temperature interval of quenching and the resulting quenching stresses. It also eliminates any changes which would take place in the undercooled sample at room temperature prior to aging at an elevated temperature. Isothermal aging is thus approached and its kinetics may be studied. An aluminum-copper and an aluminum-silicon alloy were chosen for this investigation. The aging mechanism of aluminum-copper alloys is complex while the aging of aluminum-silicon alloys is nearly ideal. As standards of comparison for the samples directly quenched to the aging temperature, specimens were also age hardened by the usual procedure in which solution treated samples are first quenched to room temperature and then reheated to the aging temperature. Review of Previous Work The mechanism of age hardening has been the subject of a controversy which has ranged from the theory of outright precipitation of an equilibrium phase to theories based on subtle changes occurring in the matrix prior to precipitation. A detailed critical review of the literature up to 1939 is available1 and contributions to the general theory of age hardening continue to be made.2,3 Age hardening, whatever its mechanism, involves the nucleation of a second phase within a supersaturated solid solution. Theoretical considerations4,5 indicate that the rate of nucleation reaches a maximum at an intermediate temperature below the temperature at which supersaturation sets in. Studies of precipitation at various subcritical temperatures have demonstrated that the largest property changes in a given time occur at such intermediate temperatures.6,7,8 The precipitation of a phase from supersaturated solid solution is accelerated by strains which may result from quenching or cold work. Phillips and Brick9 established that quenching strains are an essential condition for the age hardening of aluminum-copper alloys at room temperature, at least for aging periods of less than 30 days. They also found that on aging at 300°C the hardness increased faster and reached a higher maximum after quenching into water than after quenching directly to the aging temperatures. Fink and Smith10 observed preferential precipitation on slip bands and grain boundaries in aluminum-

Jan 1, 1950

JOHN W. BELL, *Montreal, Quebec, Canada (communication to the Secretary?). The test results in Mr. Taggart's paper will, I am sure, be recognized as a notable contribution, and of great assistance in the study of the performance of the Hardinge mill. I regret, however, being obliged to note that Mr. Taggart still retains. such confidence in the Kick-Stadler method of computing the ?relative mechanical efficiency" of crushing machines. The Rittinger-Kick graph submitted by Mr. Gates and the tests made at McGill University disclosed precisely the same fundamental defect in the Kick-Stadler theory. Consequently, I have been obliged to recalculate in terms of Rittinger surface units the results obtained in the 28 rock-crushing tests cited by Mr. Taggart, in order to find- out what the relative efficiencies really were. In order to show the large discrepancies between the Stadler and Rittinger R. M. R's, the most, efficient result disclosed by each method is represented by the number 100, and the R.. M. E.'s for the other tests have been recalculated on this basis. The results will be found in Table 1. Personally, I look forward to the time when we shall cease to talk about "relative mechanical efficiency" and merely refer to the "efficiency" of a crusher. All that is required to accomplish this is to agree on a standard method for determining the "crushing constant" of a given rock and a standard method for calculating the efficiency. The figures in the fourth column of Table 1 have been derived by assuming a constant of 2,000 for the quartzite crushed in the Yale tests. The Stadler method sometimes indicates changes in efficiency produced by, changes in operating conditions, as I pointed out in a paper describing rock-crushing tests made at McGill University. It is, however, not enough to determine that certain changes increase or decrease efficiency; surely it is equally important to determine the magnitude of these variations. By examination of Mr. Taggart's results, I have been obliged to conclude that the size of feed and amount of reduction greatly influence the Stadler R. M. E. figures, that they are positively misleading. It should be mentioned that since the majority of the tests have been made at the least efficient feed rates, and since, moreover, it is one of the evidently very important factors affecting efficiency, it is possible that different results might be obtained by a high-tonnage feed series, and that

Jan 8, 1917

By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By d&apos, L. Berenbaum, F. Heurle, R. Rosenberg

The structure of aluminum films obtained by evaporation was studied by electron microscopy, mostly by replica techniques and X-ray diffraction. The resistivities and stress conditions of the films were also determined. Film properties were studied as a function of source selection, substrate type, residual pressures of oxygen and water vapor, substrate temperature, and rate of growth. The formation of abnormal localized growths and whiskers resulting from annealing treatment subsequent to deposition was investigated. Films deposited onto single-crystal substrates were found to be epitaxially 0riented; for such films, relative orientations between films and substrates were determined. ALTHOUGH wide use has been made of evaporated aluminum films for the formation of conducting lines on semiconductor devices, relatively little has been reported concerning the structural characteristics of such films.1"9 The purpose of this study was to obtain an overall view of the dependence of these characteristics on film deposition and subsequent annealing conditions, which were similar to those used in silicon planar technology. Accordingly, most of this study was carried out using oxidized and bare silicon wafers as substrates, although some work was also done using alkali halide, magnesium oxide, and mica substrates. However, the main concern remained pragmatic. Emphasis was given to the study of the effects of deposition and annealing conditions on film characteristics such as structure, resistivity, and stress. I) EXPERIMENTAL PROCEDURES The films which were investigated in this study were deposited in 18-in.-diam glass chambers which were connected to the usual type of trapped diffusion pumps filled with silicon oil. Through the use of liquid-nitrogen-cooled Meisner traps and titanium sublimation pumps placed inside the deposition chambers, the pressure could be lowered to the lower portion of the 10- I Torr range and little increase in pressure would occur during the deposition cycle. Unless described otherwise, the substrates were 1-in.-diam p-type silicon wafers having a resistivity of 10 ohm-cm. The wafers were oxidized in wet oxygen at 975°C followed by a short dry-oxygen exposure at the same tempertture to a total oxide thickness of approximately 6000A. The wafers, backed by a layer of gallium, were mounted onto molybdenum discs brazed to a copper block.10 The latter was heated by imbedded commercial cartridge heaters. The substrate temperature could be maintained to within +10°C of a prescribed temperature during film deposition. The search for a satisfactory source for the controlled evaporation of aluminum has led to the use of 1-in.-diam crucibles" machined from rods of a commercially available, refractory composite* of Bn and

Jan 1, 1969

By L. A. Willey

Although the interierometric method for the determination of length changes was devised by Fizeau more than three quarters of a century ago, it has not achieved the widespread use in the metallurgical field that its precision and simplicity would seem to warrant. The interferometer and the basic principle are both very simple. When optically plane surfaces held at a very slight angle to each other are illuminated by monochromatic light, rectilinear, equally spaced interference fringes arc formed. Each fringe corresponds to a defiuitc thikness of the wedge formed by the optical flat.;. The difference in wedge thickness between two consecutive fringes is cqual to one half the wave length of the illuminating light. Instruments for vicwing the intertero~ncter have passed through a number of modifications. Outstanding among the improvements were those Abbe. in 1884. His improved instrument permitted micrometric mcasurements to the order of one-hundredth of the width of an interference fringe (i.e., lengths were measured to the order of one two-hulldredth of the mave length of light ). It also permitted the consecutive use of light of several wave lengths. which made possible the determination of the order number of any fringe and therefore the absolute thickness of the wedge at any point. The Abbe dilatometer and methods of measuretment, including corrections to he applied for the change of index of refraction with change in tempcrature and barometric pressure in an air wedge, have been thoroughly described by Pulfrich.' Pulfrich2 made further improvements in the interference measuring apparatus. His instrument embodied all the features of the Abbe dilatometer but was made more versatile by its complete mechanical separation from the interferorneter. The introduction of an Amici prism in the piece permitted the simultaneous observ tion of the whole set of fringe systems developed in the interferometer from the visible light of a geisler tulle. .Also, the introduction of a direct-vision, reflecting prism made it possible to set the fringes parallel to the two vertical fiducial line. of the instrument without the necessity of rotating the interierometcr. Interferometric methods employed ill this country have been developed and dcscribed by Priest, Pelers and Cragoe," Austin,5 Merritt,= Saunders,? and Nix and MaNair. Since none of these authors used the type of instrument that was employed in the present investigation, they Will not be discussed here. This paper will be limited to the description of the interfernmetric apparatus and method used at the Aluminum Research Laboratories and to the presentation of data so obtained. Apparatus and Procedure A general view of the dilatometer, not including equipment for controlling and

Jan 1, 1945

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By W. E. Horst

John Dasher (Central Research Laboratory, Crucible Steel Co. of America, Pittsburgh. Pa.)— Getting spodumene to float quickly and cleanly can be a problem. The author has presented an excellent account of a valid and useful approach to the scale-up of such problem floats. This indicated advantages for doubling retention time, i.e., buying another set of flotation cells. The author states that 21 pct of the spodumene floated in 2 min in the laboratory cell, that the grade of the rougher was about 75 pct spodumene, and that the final tailing contained 4 to 12 pct spodumene in different sizes with the present cells and 1 to 9 pct spodumene with twice as many cells. About 20 years ago, this writer obtained in the laboratory the flotation of over 90 pct of this spodumene in a King's Mountain sample in 1 min at a grade of 90 pct spodumene in the rougher and a final tailing that contained only 1 pct spodumene. The methods of Norman, Ralston," and Gieseke' were used, which teach that spodumene floats quickly and cleanly if its surfaces have been properly conditioned chemically and/or mechanically prior to flotation. Although feed preparation is not discussed, the results reported indicate that it is inadequate. This writer suggests that improvements in this area might be more effective than doubling the number of cells. W. E. Horst (author's reply)—Dasher's comments are appreciated by the author and require some clarification. He suggests that improved spodumene flotation performance may be obtained by feed preparation techniques rather than increased retention time in flotation. Certainly flotation performance is dependent on feed preparation and this is an important feature in the flotation process. It is true that certain types of spodumene ores, particularly weathered ores, require more complicated feed preparation processing than clean ores to achieve the desired flotation results. It was not implied that current feed preparation techniques are the same as experienced during the scale-up investigations. Although discussion of feed preparation was omitted from the article on scale-up relationships, the important feature was that pre-treatment processing was the same for each level of operation investigated— laboratory, pilot plant, and plant scale. Under these similar conditions large differences existed in recovery for comparable time intervals in each scale of operation. It is highly probable that feed preparation techniques could be modified and thereby increase the flotation rate for each scale or all scales of operation discussed. However, modifications would have to be justified on an economic basis.

Jan 1, 1960

Joseph William Richards, was born in Oldbury, Worcestershire, England, on July 28, 1864, of English-Scotch parents, Joseph and Bridget (Harvey) Richards. In 1871, he came to this country with his parents. He attended the public schools of Philadelphia, Pa., where his father was a manufacturing metallurgist, and in 1882, graduated from the Central High School with the degree of A. B. The same year he entered Lehigh University, from which he received the degree of A. C. (Analytical Chemist) in 1886; M. S. in 1891, and Ph. D. in 1893. His connection with the university was continuous from 1887 until his death, and he therefore adds another to the list of names of men Prominent in the A. I. 11. E. who have helped to develop Lehigh University to the important position which it now occupies in mining and metallurgical education in respect of world-wide fame. It is fitting to recall in this connection that, Eckley B. Coxe, a fonnder of the A. I. M. E., four times its vice-president,, and president in 1878-79, was literally a pillar of the university for several years prior to his death; Thomas M. Drown, founder, vice-presi(lent, secretary for 11 years, honorary member, and president in 1897, was president of Lehigh University from 1895 to 1904; and Henry S. Drinker, founder, manager, vice-president, and honorary member, was president of the university from 1905 to 1920. Doctor Richards was no less active in both institutions. With the exception of the years 1886 to 1887, when he was superintendent of the Delaware Metal Refinery of Philadelphia, his professional life was devoted to the upbuilding of the metallurgical department of the university, in part through his continuous services as a member of the teaching staff, and in part through the international renown won for the department by his achievevements as author, investigator, expert and rerognizcd authority in metallurgy, especially the metallurgy of aluminum, metallurgical-chemical calculations, and electrometallurgy. He was assistant instructor in metallurgy and blowpiping in 1887; instructor, 1888-90; instructor in metallurgy, mineralogy and blowpiping, 1890-97; assistant professor, 1897--1903; professor of metallurgy, 1903-1921. He died at his home in Bethlehem, Pa., on Oct. 12, 1921, of heart failure. To the A. I. M. E., for a continuous period of a dozen years, his services were equally loyal and effective. He was vice-president, 1910-11, and 1916-17; councilor, 1912; dirctor, 1913-15; chairman of the Iron and Steel Clommittee, 191-1-21; he was one of the framers of the Insti-

Jan 1, 1922

Joseph William Richards, was born in Oldbury, Worcestershire, England, on July 28, 1864, of English-Scotch parents, Joseph and Bridget (Harvey) Richards. In 1871, he came to this country with his parents. He attended the public schools of Philadelphia, Pa., where his father was a manufacturing metallurgist, and in 1882, graduated from the Central High School with the degree of A. B. The same year he entered Lehigh University, from which he received the degree of A. C. (Analytical Chemist) in 1886; M. S. in 1891, and Ph. D. in 1893. His connection with the university was continuous from 1887 until his death, and he therefore adds another to the list of names of men Prominent in the A. I. 11. E. who have helped to develop Lehigh University to the important position which it now occupies in mining and metallurgical education in respect of world-wide fame. It is fitting to recall in this connection that, Eckley B. Coxe, a fonnder of the A. I. M. E., four times its vice-president,, and president in 1878-79, was literally a pillar of the university for several years prior to his death; Thomas M. Drown, founder, vice-presi(lent, secretary for 11 years, honorary member, and president in 1897, was president of Lehigh University from 1895 to 1904; and Henry S. Drinker, founder, manager, vice-president, and honorary member, was president of the university from 1905 to 1920. Doctor Richards was no less active in both institutions. With the exception of the years 1886 to 1887, when he was superintendent of the Delaware Metal Refinery of Philadelphia, his professional life was devoted to the upbuilding of the metallurgical department of the university, in part through his continuous services as a member of the teaching staff, and in part through the international renown won for the department by his achievevements as author, investigator, expert and rerognizcd authority in metallurgy, especially the metallurgy of aluminum, metallurgical-chemical calculations, and electrometallurgy. He was assistant instructor in metallurgy and blowpiping in 1887; instructor, 1888-90; instructor in metallurgy, mineralogy and blowpiping, 1890-97; assistant professor, 1897--1903; professor of metallurgy, 1903-1921. He died at his home in Bethlehem, Pa., on Oct. 12, 1921, of heart failure. To the A. I. M. E., for a continuous period of a dozen years, his services were equally loyal and effective. He was vice-president, 1910-11, and 1916-17; councilor, 1912; dirctor, 1913-15; chairman of the Iron and Steel Clommittee, 191-1-21; he was one of the framers of the Insti-

Jan 1, 1922

By P. R. Kalischer

IN the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more components that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. Since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measurements and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. NATURE AND REMOVAL OF SURFACE BARRIERS The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 per cent Fe, 50 per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However, this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°°F.) for 15 min., cool rapidly to casting temperature, and cast.1 In Germany superheating is carried out at 850° to 900°C. (1560° to 1650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (1740°F.).2 In the United States superheating is carried out at i600° to 1700°F. (871° to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.§ in heavy sections and from 60 to l00 in 3-in sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. MATERIALS AND METHODS The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 per cent aluminum, 2 per cent zinc, and 0.r per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°F.) for 15 min., cool rapidly to casting temperature, and cast.' In Germany superheating is carried out at 850' to 900°C. (1560° to I650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (I740°F.).2 In the United States superheating is carried out at 1600' to 1700°F. (871' to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.! in heavy sections and from 60 to IOO in 1/2-in. sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. Materials and Methods The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 Per cent aluminum, 2 per cent zinc, and 0.1 per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By A. M. Gaudin, F. W. Bowdish

MINERAL dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,7 its magnetic remanence,3 the turbidity of its suspension,8 and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid-both internal and external-the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample .2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. APPARATUS In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. 1 and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1944

By Harry M. Mikami

Refractories are heat-resistant, generally nonmetallic materials used as the linings of furnaces or high temperature vessels in the steel, iron, nonferrous metals, glass, cement, lime, ceramic, chemical, petroleum, paper, and power and heat generation industries. Refractories must have structural strength at high temperatures but also, in many applications, must simultaneously resist chemical-physical corrosion-erosion from stags, metals, granular solids, or gases. Among the major uses are the pyrometallurgical processes for producing iron, steel, copper, aluminum, nickel, lead, zinc, etc. Rotary cement kilns, glass tanks, refineries, utility boilers, chemical and ceramic (including refractories) plants, and a myriad of other smaller scale users employ refractories in the high temperature parts of their operations. Thermal, chemical, and structural conditions under which refractories are used differ widely so there is a great variety of refractories to fill the various needs. Two major classifications are the "basic" and "acid" types. Basic refractories include magnesia and chromite, singly and in combinations, dolomite, and forsterite (olivine). The acid category includes aluminosilicates, alumina, and silica. There are a number of other specialized types such as carbon, graphite, silicon carbide, zircon, and zirconia that have important applications but are used in much smaller amounts than the major categories. Physically, refractories can be divided into bricks and shaped products on the one hand and unshaped or monolithic products (also termed specialties) on the other. There are many further subclassifications and divisions, a discussion of which is beyond the scope of this chapter; see Refs. 2 and 9. Raw materials for the principal basic refractories are magnesia and chrome ore. Magnesia, generally termed magnesite or periclase, is obtained mainly from seawater or saline brines extraction, but substantial amounts are produced from mined magnesite (MgCO3). Dolomite (CaCO3•MgCO3), another important basic refractory, is obtained entirely from mined sources. Acid refractory raw materials are: fire clays, flint clays, kaolin, and other natural clay minerals; aluminosilicate minerals such as kyanite, andalusite, sillimanite, pyrophyllite, bauxitic clays; calcined refractory grade bauxite, alumina from the Bayer process for the alumina group; and quartzitic rocks for silica refractories. The total value of all refractories shipped in the United States in 1974 was $989 million, a record to that date. Of this amount, about 73% represents bricks and shaped products and 27% is in nonshaped or monolithic products which comprise mortars, cements, castables, plastics, and ramming and gunning mixes. Fig. 15.4E.1 shows the rising value of all U.S. refractory shipments in the period 1948-1974. Values of brick and shapes paralleled

Jan 1, 1976