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By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

JUST as I have taught you to refine silver in a small way and to make assays, so now I wish to teach you how to make cupeling hearths in place of these little cupels when you have silver in large quantities. This is done in four ways, as I have seen, but all are alike in the end and differ very little one from the other. There are some who make use of a furnace with a vault built with bricks above the cupeling hearth. There are some others who use in place of this an iron hood like a large cover. There are some others who use only heavy dry sticks of oak or some other thick wood. Others have certain long plates of terra cotta that cover the whole hearth in three or four pieces; the two of these that adjoin have [56] a hole in the middle that leads exactly into the middle of the cupeling hearth, and through this they put in the material and the lead, according to the practice I shall describe.

Jan 1, 1942

By Robert Steinitz

Soft iron parts for magnetic applications, particularly pole shoes, constitute a major portion of the ferrous products of powder metallurgy. The residual pores in pressed and sintered parts reduce values such as the magnetic permeability but service experience extended over a number of years has proven beyond doubt that in many instances the lower density of powder parts is not prohibitive to their use as replacement of machined magnetic parts. The magnetic requirements for pole shoes, particularly the permeability, vary within wide limits, especially with the relative size of the air gap in the finished assembly. The overill permeability of an assembly, is given by the formula where is the permeability of the core material, I the total length of the magnetic path, and a the length of the air gap. Fig I shows the variation of the overall permeability with the permeability of the core material, calculated according to Eq I for an air gap of I pct of the total length of the magnetic circuit. It is readily recognized that to use core materials hav- A

Jan 1, 1949

CAMBRIDGE, MASS., May 22, 1913. TO THE PRESIDENT, American Institute of Mining Engineers. Dear Sir: Referring to Mr. J. WV. Finch's letter printed in the Institute Forum of the May Bulletin, I am very much in sympathy with his suggestion that the Transactions be printed in several volumes devoted separately to the various subjects covered by the Institute papers, such as " Iron and Steel," "Mining Geology," " Precious and Base Metals," etc. The advantages of this plan appear to me so great and so obvious as to far outweigh any possible objections. At a meeting of the Iron and Steel Division Committee held on June 28, 1912, I moved that the Committee recommend to the Council that papers on Iron and Steel be published in separate annual volumes. The motion was seconded and passed. Since then I have never failed to repeat my request whenever an occasion presented itself, and I welcome the opportunity offered by Mr. Finch's communication to again call the attention of those interested to an innovation which appears to me so highly desirable. ALBERT SAUVEUR.

Jan 6, 1913

By Jack Fox

Last time there was a Take Five in these pages, it dealt largely with the matters considered by your Board of Directors at the meeting on October 20, 1970, in St. Louis, Mo. It was impossible to cover all the points worthy of discussion in the space available. So, at the end of the Take Five in the December issue of [i=], I promised to continue in the next installment. Unfortunately, I was unable to keep that promise. On December 2 your humble servant joined the ranks of those who have suffered a coronary occlusion. While I was away from the office, the very excellent SME staff team that we have built up over the years kept things going without bothering the "old man" unnecessarily. Assistant Executive Secretary, John V. Beall, Mrs. Lillian E. Donaldson, Assistant to the Executive Secretary, Mrs. Ruth Orologio, Administrative Assistant, and Mrs. Alice Ruiz exceeded even their usual dedicated efforts. As a result, the SME came up to the Centennial-Annual Meeting in great shape.

Jan 1, 1971

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10' dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By Jo. E. Sheridan

The Dawson coal-mines are owned aid operated by the Stag Canon Fuel Co., of which Dr. James Douglas is President and E. L. Carpenter general manager. The property is situated in Colfax county, N. M., and the openings now in operation are in townships 28 and 29 N R. 20 E., and township 28 N E. 21 E., shown in Fig. I. The mines are part of the southern end of the Raton coal-field, which extends north into Colorado and embraces many coal-camps of the Trinidad section. II. Geology. Geologically, the coal-measures, commonly known as the Laramie series of the Cretaceous system, have x thickness of about 800 ft. in the vicinity of Damson. The coal makes an excellent coke, and, according to some authorities, its coking properties are due to the action of intruded sheets and sills of igneous rock, the sheets occasionally thickening into masses resembling laccoliths, at such places making nearer approach to the coal and sometimes producing small areas of natural coke. There are but few dikes throughout the entire southern portion of the field and little or no faulting along the dikes. In some parts of this great coal-field the intrusive sheets are far removed in the green shales below the coal-measures, and are so much altered as to be difficult of identification. There is but little disturbance of the strata throughout the Raton coal-field in as far as it extends into New Mexico. There are two workable seams in the coal-measures, and two or three smaller coal-seams, ranging from 1 to 2.5 ft. in thick-

Jan 1, 1910

By C. Feng, I. R. Kramer

A study was conducted to determine the influence of the surface on the yield point of fcc metals and high-purity iron. For the high-purity fcc metals, the yield Point produced by restraining a specimen may be eliminated by removing a sufficient amount of the layer. A yield point similar to that in fcc metals was found when iron specimens were pre-strained after a prior deformation. This yield point is not due to an aging effect but is associated with the surface layer. The yield points in age-hardenable aluminum alloy and those connected with "work softening" are not affected by a surface-removal treatment and are, therefore, caused by bulk-type dislocation reactions. The yield point which appears in previously strained fcc metals has been the subject of numerous studies. Several theories have been advanced to explain this "unloading-reloading" yield point. Cottrell and stokes,' from their study on the effect of temperature on plastic properties of high-purity aluminum, considered that it was the result of an avalanche "breakdown" of Lomer-Cottrell sessile dislocations. Haasen and Kelly2 extended this concept of dislocation-dislocation interaction to account for the yield point when unloading and reloading was carried out at the same temperature. On the other hand, strain aging was found to be responsible for the yield point in A1-Mg alloy by Westwood and Broom,3 and in aluminum alloys containing various amounts of alloying elements by Smallman, Williamson, and Ardley.4 In these cases, the yield point is considered to be associated with the locking of dislocations by impurity atoms. Birn-baum and filer5,6 and Takamura and muira7 reported that, when a high-purity copper specimen was prestrained, then held at a lower stress, and finally reloaded at the prestrain temperature, a larger yield point was observed. Such an increase was attributed to the locking of dislocations by point defects. In addition, Bolling8 suggested that both mechanisms, i.e., dislocation-dislocation interaction and strain aging, are responsible for the yield phenomenon, at least in a brass. Thus, there appears to be experimental evidence for both the strain aging and dislocation-dislocation interaction theories to explain the yield point in the fcc metals and alloys. In a previous article,9 one of the authors observed that, if sufficient amounts of metal were electrolti-cally removed after deformation of a high-purity aluminum single crystal, the yield point did not appear upon reloading. Continued pursuit in this area revealed that the effect of the surface on the yield-point phenomenon is not limited to one metal but affects a variety of metals of different lattice structures. Nor is the effect limited to the yield points produced by simple unloading-reloading at constant temperature; the surface exerts an important role on the yield point even when the temperature is changed at some stage during the test. It is the intent of the present article to give additional information regarding the effect of the surface on the yield-point phenomenon and to show the association between the yield point in both fcc and bcc metals and the existence of a heavy concentration of dislocation in the region near the surface of a deformed specimen.10 EXPERIMENTAL Materials. The single crystals used in this study had a nominal cross section of 0.125 by 0.125 in. and a 3-in. gage length and were prepared by a modified Bridgman technique. The initial purity for the metals was 99.997, 99.999, and 99.999 pct for aluminum, copper, and gold, respectively. Bar stock of these same materials was used in the preparation of the polycrystalline specimens of aluminum and copper. The iron specimens were machined from rods of "ferrovac", reported to have a purity of 99.98 pct. In addition, a precipitation-hardening aluminum alloy, containing 1.5 pct Cu, 2.5 pct Mg, and 5.5 pct Zn, was used. The polycrystalline specimens of iron, copper, and the aluminum alloy had a diameter of 0.17 in. and a gage length of 2 in. while the high-purity aluminum specimen had a nominal rec-

Jan 1, 1965

By BION J. ARNOLD

WE can, I think, rightfully claim, irrespective of our faults, that engineers must, in order to last as engineers, possess the qualifications of integrity, stead- fastness of purpose, ability to think straight, and to apply these qualities consistently and continually in their everyday work. All engineers know this, most of them conform, and in order to drive it home I might, if 'clothed with proper authority, preach to you at length, but I shall not take the chance. So I only want to make a suggestion or two to the young engineers. Have an ideal and work toward it. You will have your disappointments and your temptations but keep your record clean, and if anyone says you are foolish or ugly, or homely, or that you need a guardian, take the criticism with a smile, for he may be able to prove his contention; but if he attacks your integrity, strike at once and fight hard, for he has assailed not only your character but your principal asset as an engineer.

Jan 1, 1929

By W. H. Bassett, J. C. Bradley

In considering the effects of reducing gases on hot solid copper the following conclusions have been reached. (I) Depth of deoxidation of copper heated in reducing gas is grealer the smaller the amount of cuprous oxide originally present in the copper, the range studied being from 0.015 to 0.136 per cent. oxygen. It is suggested that the reason for this diflerence in depth of deoxidation is thai, when the copper is low in cuprous oxide, the reducing gas is diluted less by the gas that is formed in the reaction than when the copper is high in cuprous oxide; and the greater the concentration of the reducing gas the deeper the deoxidation. (2) The rate of deoxidation is much more rapid at the beginning of exposure than at the end, a condition especially noticeable at temperatures around 900" C.; that is, deoxidaion is retarded as the depth penetrated by the reducing gas increases. (3) Within the accuracy of the experiments arsenic in copper up to 0.5 per cent. has no tendency to increase or decrease the action of a reducing gas on the cuprous oxide presenx in the copper. In 1912 pieces of 0.365-in. hard copper rod 1/2 in. long were heated in a porcelain tube in an electric furnace, while illuminating gas was passed through. An approximate analysis of this gas is: Hydrogen 38 per cent., carbon monoxide 30 per cent., illuminants 13 per cent., methane 10 per cent., ethane 3 per cent., carbon dioxide 3 per cent., nitrogen 2 per cent., oxygen 0.4 per cent. After heating for various lengths of time at various temperatures, samples were quenched

Jan 1, 1926

By J. H. M. Thomeer

A method is presented that provides a mathematical description of capillary pressure curves and, probably, of differences in pore geometry of samples. The technique is based on the observation that the location and shape of a capillary pressure curve reflect characteristics of the pore structure of the sample. INTRODUCTION It has been noted1-5 that the observed differences in shape and location of capillary pressure curves reflect some basic properties regarding the pore geometry of the samples. For example, according to basic concepts of capillarity, the following statements can be made regarding the location and shape of a capillary pressure curve.* The location of the curve with respect to the (Vb)pc and PC axes is a measure of the interconnected pore volume and of the cross-sectional area of the pore first entered by mercury, respectively. The shape of the curve depends on the interconnection of the pores and the sorting of the pore sizes. It has been the object of this study to use this information as a starting point in an attempt to find a unique mathematical description of the PC — (Vv)p, relations of different samples. It may be expected that parameters in such a relation can then be used to describe differences in pore geometry of these samples. For a practical description of the PC — (Vb)p, relation, however, it appears desirable to describe each curve (i.e., each sample) by a limited number of parameters so that the curves taken from all samples form a family, each member of which is uniquely determined by one single combination of values of all parameters.

By H. R. Hose

Total crude fluorspar reserves in western Europe, containing more than 35 pct CaF*, are estimated at 12 million metric tons, while reserves in the USSR and Soviet sphere may exceed 5 million metric tons. The bulk of these reserves are concentrated in the USSR, Spain, United Kingdom, Western Germany, and Italy. Since published estimates of the tonnages of individual mines and explored deposits are not available for most countries in Europe, the estimates given in Table I for individual countries are necessarily approximate, as they have been compiled from various sources and modified and combined according to the author's judgment. The majority of fluorspar deposits in Europe belong to the late Paleozoic metallogenetic epochs and have been found within or along the borders of the Hercynian massifs. Deposits in the Central and Esterel massifs of France, those of Western and Eastern Germany, Sardinia, the Catalonian coastal range and the Sierra de 10s Santos in Spain, and those of Devonshire and Cornwall belong to the Hercynian metallogenetic epochs. The deposits in southern Norway and Sweden belong to the middle Paleozoic or later, those of northern England to the late Paleozoic or later, those of northern Spain and Greece to the late Mesozoic, and those of northern and probably central Italy and Switzerland to the early Tertiary. Fluorspar occurs typically in veins, lenses, and stringers, but also in bedded replacement deposits and pockets, and may be colorless to white, yellow, green, pink, brown, blue, or purple to almost black. Except for the colorless variety, the only kind which can be used for the optical industry, the color of the fluorspar does not affect its ultimate use,

Jan 4, 1955

By A. C. Heath, E. H. Dix

THE importance of aluminum-silicon alloys in the light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and like silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminum and aluminum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. PART I.-ALUMINUM-SILICON ALLOYS The early work on this system was largely confined to determining the general form of the diagram and in this respect the results are in good agreement. Briefly, aluminum and silicon form a simple eutectiferous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Fraenkel1 (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solution. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility does not appear

Jan 1, 1928

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967