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By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By James Boyd

In critical times such as the present, when the whole world is agitated by the aftermath of war and the road to peace is blocked by seemingly insurmountable obstacles, it is fitting that we should pause to take inventory of the material resources essential to our national security. Our status as a world power, in peace as well as in war, is intrinsically bound to the availability of minerals, for the foundation of our industrial and economic structurewhich in turn largely determines our military potential and our limits of national prosperity-rests on our ready access to economic sources of iron, copper, lead, zinc, manganese, bauxite, and at least threescore of other metals, minerals, and mineral fuels. By applying the well-known facts of mineral resources to recognized fundamental concepts of preparedness, we can obtain a- clearer picture of the essential needs of our country. Historically, the lure of minerals and other raw material resources has all too frequently led nations to policies of imperialism and war. For more than a century the staking of colonial territory for new sources of raw materials has been a primary objective of many nations. These national policies. of aggrandizement were accelerated by increasing industrialization. The nations, in their aggressive search for

Jan 1, 1948

By R. W. Harper, M. C. Fuerstenau, J. D. Miller

Data were obtained with hematite with octyl hydroxamate and oleate as collectors to determine the mechanism of collector adsorption and also to establish the roles that conditioning time and temperature assume in this system. The presence of hydroxy complexes of iron are apparently necessary for chemisorption of collector to occur, and it appears as if extended conditioning times and elevated temperature promote greater dissolution of the mineral and hence greater concentrations of hydroxy complexes. Data were also collected with two natural hematitic ores. With one ore that was ground to 70% - 15u, an addition of 0.4 lb per ton hydrox-amate resulted in a final concentrate recovery of 86% at a grade of 64% iron. Satisfactory concentrate grade could not be obtained with fatty acid under these conditions. The effect of conditioning time prior to the addition of collector was also examined with another ore. When the ore was conditioned for 3 min, 19% of the iron was recovered in the concentrate at a grade of 67% Fe. With a conditioning time of 7 min, 73% of the iron reported to the concentrate at a grade of 62% Fe. These products were obtained with an addition of 0.2 lb per ton hydroxamate. This ore also responded well to flotation with fatty acid. The use of potassium octyl hydroxamate as a collector for iron oxide has been the subject of an earlier study.1 From this initial study, it was suspected that hydrolysis of surface ferric iron was involved in collector adsorption. More recent work in other systems has shown that slight mineral dissolution, followed by hydrolysis of cations common to the mineral lattice, is apparently necessary, and that adsorption of these hydroxy com- plexes probably occurs prior to the adsorption of collector. In view of these facts, work has been continued on the hydroxamate-hematite and oleate-hematite systems to gain better insight into the mechanisms of collector adsorption on iron oxide. Microflotation experiments in conjunction with infrared analysis were used in this regard. In addition it was felt necessary to establish more clearly the responses that can be obtained from natural ores when hydroxamate is used as collector as compared to those obtained when fatty acid is used. Experimental Materials and Techniques Pure potassium oleate, potassium octyl hydroxamate, synthesized from hydroxylamine hydrochloride and methyl octanoate, and a distilled Tall Oil were employed as collectors. Conductivity water was used in the

Jan 1, 1971

By J. R. Long, T. R. Graham, R. S. Dean

FOLLOWING the development of elec¬trolytic manganese production by the Bureau of Mines, an extensive program was planned to study the character of this high-purity product and its possible utilization in various alloy combinations. Previous work reported in the literature concerning alloys containing substantial amounts of manganese dealt largely with material prepared from relatively impure grades of the metal, and in many instances the impurities thus introduced did not permit true evaluation of manganese as an alloying element. One phase of the Bureau's program included a general review of the system and the establishment of the physical properties of copper-manganese-zinc alloys, using electrolytic manganese, and with particular emphasis directed to com¬positions within the alpha solid solution area. A number of reports of the work on alloys in this system, giving specific data concerning the equilibrium system and some of its alloys, have already been published. One study1 established the alpha solid solution area at various temperature levels and composition ranges up to 50 pct manganese. Other investigation reports presented the properties of selected alloys; namely, a 65 pct copper, 10 pct manganese, 25 pct zinc alloys' a sensibly white manganese brass composed of 70 pct copper, 20 pct manganese, 10 pct zinc,3 and a series of alloys with a constant copper content of 60 pct and 5 to 25 pct manganese, balance zinc.4 In these reports tensile properties as influenced by cold-working and subsequent annealing were given in detail. Additional data are now available on other alloys of the alpha region up to 50 pct manganese, and these, together with previously published information, are sufficiently complete to establish the relationship between properties and composition for this portion of the ternary system. The present report is a summary of the tensile properties of wrought alloys in the form of sheet and rod stock. The summary is necessarily limited to data for only one condition of cold-work and a single annealing temperature, since a complete exposition of all the data available would be too extensive for this presentation. Nevertheless, it is possible to make a reasonable approximation of the tensile properties in other conditions of cold-working and annealing by a correlation of the data previously presented on specific alloys and the data given here.

Jan 1, 1947

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1'3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967

By J. B. Mackintosh

In a recent paper read before the Institute on this subject, Mr. G. C. Stone advances the theory that the precipitate obtained in Williams's volumetric process,* by treating the boiling nitric acid solution of a manganese salt with potassic chlorate., is not pure MnO2, but approximates more closely to the composition 10Mn02+Mn0. As the value of the process and the accuracy of our results mould depend on whether this was the fact or not, it has seemed to me, and to my associates, Messrs. Beebe and Colly, that it would be of importance to ascertain the composition of this precipitate, and to that end the following series of experiments has been undertaken. These experiments have all been based on the considerations: 1. That potassic permanganate has an oxidizing power equivalent to five atoms of oxygen for every two of manganese : K2Mn2O8 = K2O.2MnO.O5. 2. That the same amount of manganese in the state of binoxide has an oxidizing power equivalent to two atoms of oxygen : 2MnO2 = 2MnO.O2. If, then, we take a solution of permanganate of unknown strength, and reduce it to binoxide, the oxidizing power of the binoxide formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. While, if the precipitate obtained should not be binoxide, but an indefinite or definite mixture of bin- and mon- oxides, then, from its equivalent oxidizing power, we can calculate its composition. The analyses were conducted in the following manner. The amount of permanganate taken was decomposed with hydrochloric acid, and concentrated to expel the excess of water. Sufficient excess of nitric acid was now added, and the solution was boiled until all the hydrochloric acid was destroyed. The manganese was then precipitated by potassic chlorate; and, after standing some time to cool—a pre-

Jan 1, 1884

By Henri S. Swolfs

INTRODUCTION In this paper we present preliminary results of a research program in site characterization methodology. We are interested in under- standing the response of discontinuous rock to mechanical, hydrologic, and thermal loadings. To carry out such a study we selected a field site with simple geology, uniform distribution of lithologies, and easily verifiable boundary conditions on temperature, fluid flow and stresses. The spatial distribution of fractures at the site was established and tests were conducted to determine the temperature field, hydrology, rock-mass properties, and in situ stresses. As part of the study selected borehole instruments were compared to assess their performance and reliability. SITE GEOLOGY The study area is in the eastern part of South Table Mountain, a mesa near Golden, Colo. The exposed cap rock is a single lava flow of uniform thickness (6-7 m) that rests on the clastic sediments of the Denver Formation (Van Horn, 1976). The surface of the cap rock (N. 75º E., 3º S.) is topographically featureless and slopes south- southeast; drainage is predominantly downdip and punctuated by occasional contact springs. The age of the lava flow is 64-65 m.y., or early Paleocene. Paleo- botanic evidence confirms the upper part of the Denver Formation as Paleocene (Van Horn, 1976). "Rapid-rock" analyses of core samples from the lava flow at three depths (0.2, 3.3, and 5.8 m) suggest a uniform chemical composition throughout with an increase in the Fe2O3/ FeO ratio (1.05 to 1.60) with increasing depth, reflecting the existence of a perched water table in the lava flow, To identify the rock

Jan 1, 1984

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By William M. Bowron

THIRTY years ago, when I stood on the cliff of red fossil iron-ore, on Red mountain, Jefferson county, Ala., I asked what were the geological relations of this remarkable deposit. In reply I was told that it was a limestone colored and saturated by some unknown but wholly external influences, and that at a reasonable distance from the surface the color would disappear. I could find no satisfactory explanation either of the nature of this wonderful external permeating influence, or of the cause of such a ferrous impregnation selecting this one particular bed of limestone, to the exclusion of the higher and lower beds of the same material which are not even stained. I. THE PRESENT THEORY. Referring to this subject, Dana says:' "The clays, clayey sandstones and limestones of the Clinton epoch, through New York and the Appalachians, show that the mud-flats and sand-banks, and hence the shallow seas of the coast region, still continued. . . The beds of argillaceous iron-ore, which spread so widely through New York and some of the other States, south and west, could not have formed in an open sea, for clayey iron-deposits do not form under such circumstances. They are proof of extensive marshes, and, therefore, of land near the sea-level. The fragments of crinoids and shells found in these beds are evidence that they were, in part at least, salt-water marshes, and that the tides sometimes reached them." At first, this explanation seemed satisfactory, but the more I studied the ore the less satisfying the explanation became. 1. In the ore itself I found associated with the small particles of rounded matter (now consisting of iron oxide in which organic structure, if ever present, has become lost, though the

Nov 1, 1905

By Samuel B. Christy

At the last meeting of the Institute, several contributions were made to the subject of miners' aid funds. Such matters will always form important factors in the administration of large industrial enterprises. From the frequently remote and isolated position of mining properties, it is a subject that often forces itself upon the attention of the mining engineer. Local conditions are usually so variable that no single method can be found equally well adapted to all localities. At the same time, a study of different types is often suggestive and valuable, and it is with this in view that these notes are presented. The Miners' Fund of New Almaden is a remarkably successful example of what may be done for miners by a wise and at the same time firm management, by simply directing their own efforts and without incurring any great expense to the stockholders,—a practical consideration not without importance in most cases. The quicksilver mines of New Almaden are situated at a distance

Jan 1, 1885

By Robert F. Brindisi

There are approximately thirty to forty operating mills in the United States which are currently producing uranium yellow cake. This figure includes a significant number of in situ and by-product operations however the conventional acid leach flowsheet depicted in Figure 1 is the most common process used by domes- tic yellow cake producers. Ground ore is leached with sulphuric acid and the solids are separated from the pregnant liquor and washed in a series of counter- current decantation thickeners. After clarification of the pregnant liquor, uranium is recovered from the solvent extraction/stripping circuit by the addition of ammonia with precipitation of ammonium diuranate, or simply yellow cake. The yellow cake precipitate is then thickened in a conventional thickener before re- porting to the dewatering/washing unit operation. De- watered solids subsequently report to thermal drying, and clarified liquor from the dewatering/washing step is recycled to the yellow cake thickener. The yellow cake dewatering/washing unit operation is generally accomplished using either a solid bowl centrifuge or a rotary vacuum drum filter. In most cases the underflow from the yellow cake thickener is pumped to the dewatering/washing unit operation at approximately fifteen to twenty percent solids. For the purpose of this discussion ammonium diuranate, the product of ammonia precipitation from a conventional acid-leach uranium mill flow sheet, as discussed earlier, will be considered. With only slight adjustment this discussion will be equally applicable to sodium diuranate or uranium perioxide precipitates and to either in situ or by-product operations where such precipitates are generated. Some of the domestic uranium mills which have selected solid bowl centrifuges instead of vacuum drum filters for the dewatering/washing unit operations are listed in Figure 2. Why have these uranium mills, as well as others not listed, chosen to use the solid bowl centrifuge for this particular application? It is simply a matter of performance, reliability and economics. In the remainder of this paper the performance, initial cost, installation cost, maintenance and power consumption of both the solid bowl centrifuge and the rotary vacuum drum filter will be com- pared. In order to provide a consistent basis for comparison the appropriate sized (centrifuge or filter) unit for the dewatering/washing of 400 to 500 pounds per hour of yellow cake solids will be considered. Such a flow will usually be generated by a typical 3,000 ton per day (acid-leach) uranium mill.

Jan 1, 1980

Prof. Henry S. Jacoby, Cornell University,Ithaca, N.Y. (communication to the Secretary): When a simple beam supports any given load, the lower fibers me in tension while the upper fibers are in compression, and if its cross-section is rectangular the neutral surface, where the stresses pass through zero from tension to compression, is at mid-depth, provided the elastic limit is not exceeded. In addition to the longitudinal stresses, there are horizontal shearing-stresses between the fibers which have their maximum value in the neutral surface, and which equal zero at the upper and lower surfaces, while there are also vertical shearing-stresses. Let another beam of the same dimensions be placed on top of this one, and the load be doubled, it then produces stresses in each beam of the same character, magnitude and distribution as in the preceding case, provided there be no friction between the adjacent surfaces of the beams. Next let these two beams be so firmly united that there will be no motion between them when the same load is again applied. All the fibers in the upper beam are now in compression, and those in the lower beam in tension, while the maximum stresses in the outer fibers are only one-half as large as before. The strength of the combined beams is therefore doubled. If, however, some motion occurs between the beams, then the stresses in some of the lower fibers of the upper beam pass from compression to tension, and those in some of the upper fibers of the lower beam from tension to compression, while the stresses in the outer fibers have a magnitude between the two values previously stated. These fundamental facts relating to the flexure of beams indicate the necessity of carefully designing the keys or brace-

Jan 1, 1898

By AIME AIME

THE outstanding event of the past month has been the conference in Washington of the representatives of about seventy-five of the leading national, regional and local engineering and allied technical organizations." Editorial-July Journal-The American Society of Mechanical Engineers. ?Prominent engineers from all parts of the country, representing more than 75 engineering societies, with an aggregate membership of more than 125,000, participated in the organization.? Editorial-July Journal-American Institute of Mining and Metallurgical Engineers. ?Civil, mechanical, electrical, mining, heating, sanitary, chemical, agricultural, marine, refrigerating, radio, fire protection, automotive, industrial and military engineers, as well as some architects and geologists assembled at Washington, D. C. to consider the advisability of organizing a national federation capable of bringing the united efforts of the entire membership to a focus on any problem of mutual interest." American Architect, June 23, 1920. ?"the object sought places it above any engineering gathering ever held." Editorial-American Machinist, June 17, 1920. "The youngest. profession has voluntarily accepted its responsibility in human affairs and is now reaching forward to a career of essential service." "This is .unmistakably the meaning of the Organizing Conference " Editorial-Industrial Management, July; 1920.

Jan 1, 1920

By George Krauss, M. Cohen

The reverse martensitic transfomzation (i.e., the conversion of martensite to austenite on heating) was investigated in Fe-Ni alloys containing 30.5 to 33.5 wt pct Ni. The reversed austenite was found to be sufficiently distorted to exhibit marked differences in mechanical properties and to undergo recovery and re crystallization on further heating. In particular, the yield strength of the reversed austenite was as much as 2.5 times higher than that of the virgin austenite: with five cycles of the direct and reverse martensitic transformation, the yield strength was 2.6 times higher. There was an accompanying decrease in strain-hardening capacity and in stable ductility or uniform elongation. The recrystallization was observed to follow sigmoidal kinetics, but was characterized by an abnormal1y large temperature dependence which was evidently due to carbon segregation at the migrating grain boundaries. Upon recrystallization, the strength Properties reverted to those of the virgin austenite, but the ductility did not fully recover until the annealing temperature was further raised to dissipate the carbon segregation at the grain boundaries. The transformation of reversed austenite to produce second-generation martensite resulted in an unusually imperfect structure, thereby leaditg to additional strengthening. Horlleuer, the martensitic phase was much less responsive in this respect than was the austenite. MOST martensitic transformations are capable of undergoing a reverse transformation back to the austenitic phase on heating.&apos; This reaction, like the direct transformation to martensite on cooling, is usually athermal. In analogy with the Ms andMf temperatures for the martensitic transformation (where M, > Mf), the reverse transformation is characterized by the As andAf temperatures (where As<Af). It is well-known that the finish (Af) of the martensite-to-austenite reaction on heating may occur at a temperature where austenite is not stable relative to other phases in the equilibrium diagram.&apos; Reverse martensitic transformations have been found to influence the properties of the parent austenitic phase in a number of ferrous alloys. The austenite thus produced after one or more reversals is significantly altered in strength, microstruc-ture, diffusivity, and annealing characteristics compared to well-annealed, virgin austenite. The first detailed observations of such phenomena were made by Wasserman3 on an Fe-30 wt pct alloy. He found that the reversed austenite (i.e., austenite formed by the reverse martensitic transformation) was much stronger than the original austenite, and the second-generation martensite (i.e., martensite produced from the reversed austenite) was somewhat stronger than the first-generation martensite. On heating the reversed austenite, recrystallization occurred in a manner similar to that of a cold-worked metal; the Laue spots sharpened and the strength decreased.4 In recent years, Russian workers have shown considerable interest in these reverse martensitic transformations. Most of such investigations5-10 have been concerned with the stabilization of reversed austenite relative to subsequent martensitic transformation, and because of its unusual nature, this phenomenon will be discussed in detail elsewhere." On the other hand, the annealing behavior of reversed austenite and the attendant variation in properties have received little attention beyond the experiments of Wasserman.3,4 Gridnev eta1.,8 in one of the few such studies. followed the hardness change of reversed austenite as a function of time at three annealing temperatures. The marked strengthening of austenite achieved by the reverse martensitic transformation has been referred to as "transformation strengthening" by Wasserman3,4 and as "phase hardening" by Malyshev et a1.7,9,10 to differentiate it from hardening produced by cold working. Both groups of investigators noted that further strengthening of the austenite could be attained by repeated or cyclic transformations, but the first cycle resulted in the most pronounced effect. Evidence of the altered microstructure of reversed austenite has been reported by Maximova and Nikonorova6 and by Edmonson and KO.12 The former found that reversed austenite was much more sensitive to etching than the original austenite, and the latter authors observed a (&apos;ghost" structure resembling martensite in certain areas of the reversed austenite. Enhancement of the self-diffusion rate in reversed

Jan 1, 1962

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."&apos; These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen&apos; has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell&apos;s12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova&apos;~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By John T. Thorndyke

MOST important of the naturalcalcium silicates is the meta¬silicate, CaSi03, known as wollastonite, after W. H. Wollaston. A large deposit of this mineral was dis¬covered some seven years ago near Code Siding, Rademacher mining dis¬trict, Kern County, Calif., the deposit being some 7500 ft. long and of an average width of 300 ft. It consists of a series of small domes striking north¬erly and southerly and with a dip of 81 ° to the south. This deposit was opened up by a series of small quarries showing a potential tonnage of 12,000,¬000 tons, allowing of cheap mining and transportation, the Southern Pa¬cific R.R. spur track being one mile north of the workings. Numerous sam¬ples taken from different points on the deposit, tested by Mr. Brinker, of the California Testing Laboratories, Los Angeles, showed an average as fol¬lows: Per Cent Silica (SiO2) 47.12 Lime (CaO) 41.72 Magnesia (MgO) 2.72 Alkalies (R,0) Trace Iron (Fe.,O,) 1.60 whereas the theoretical composition of of wollastonite, as given by William Shirley Bayley, is as follows: Silica 51.75 Lime 45.25 The tonnage and purity of this de¬posit led to investigations into its com¬mercial development. Early work es¬tablished the fact that wollastonite was ideal for the manufacture of a tough, almost unbreakable, glass similar to Pyrex. It also established the fact that wollastonite was particularly adapted for use in the manufacture of mineral wool, towards which further research was then directed. Briefly, the prin¬cipal advantages were the substantially unvarying chemical composition of the naturally occurring mineral and its characteristic of being relatively flexi¬ble and highly resilient when fused into a glass. A mineral wool produced therefrom is thus not only of highly uniform composition and color but is most desirable because of the high mechanical strength and length of the individual fibers constituting the wool. It is well known that mineral wool may be prepared by melting a suitable charge of raw material and then intro¬ducing a stream of a suitable fluid, such as air or steam, into a stream of the molten raw material. By this means the molten material is blown into threads or fibers, which are collected in a suitable chamber similar to a tun¬nel, from which they are removed from time to time or continuously. Com¬mercial manufacture of mineral wool has been carried on for only about 50 years, but volcanoes, specifically Kilauea in the Hawaiian Islands, have

Jan 1, 1936

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit &apos;flash&apos; chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om&apos;nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.&apos; One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.&apos; By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

K. W. Turner, Sail Francisco, Cal. (communication to the Secretary*): The recent papers in the Transactions by Vogt,&apos; Lindgren2 and Weed: on ore-deposits that have formed as a direct result of igneous intrusions, show that deposits of this class are widely distributed over the world, and are occasionally of commercial value. This is especially true if we consider under this head all deposits in the zone of contactrnletamorphism, the origin of which may be ascribed to the gases and vapors generated by the heat of the intrusive rock. Mr. Smith&apos;s description of the Chillagoe garnet-formations containing copper, leads one to regard these depoaits as of contactrmetamorphic origin, although he gives certain reaeons for supposing them to be of igneous origin.

Jan 1, 1904