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By Persifor Frazer

These properties, owned by Mr. William A. Butcher, of Philadelphia, are in the Panuco Mountain, which lies about thirty miles southwest of the town of Candela. It is a granite which penetrates the surrounding limestones and contains the famous copper-mine to which it gives its name. This mine, which is the property of a company in Philadelphia, has long been known to produce gold as well as copper from almost all its parts; and in corroboration of this be it said, that the undersigned has washed gold from a number of places where the works of the mine or natural sections had exposed the decomposed granite to view in the state of kaolin. It is well known that these junction- or contact-planes between two different formations are often the lodging-places of much freemilling gold, which through fissures are sometimes carried long distances perpendicular to the strata and into the interior of the formation. The structure of the Panuco Mountain, with its outlying spurs and adjacent foot-hills, forms a most instructive and unusual study. At a rough guess the area covered by this mountain will equal, perhaps, twenty-five to thirty square miles ; but its singular feature is the intimate welding together of two formations into one topographical unit. The lines of division between the granite and the calcareous sandstone are of such complicated character that they could not be mapped on a small scale. Unlike the majority of such contacts, the divisions between formations are not always marked in the Panuco Mountain by gulches, valleys, and streams (or the dry beds of the latter), but in the portion of the mountain which lies south of the Panuco copper mine, the lines of junction of these formations cross the gulches and promontories, and, in some instances, cannot be traced by any such topographical features. The house of the Panuco copper mine is 3742 feet above oceanlevel (by rough barometric observation), and the gold-mine about to be described is 235 feet above this, and about two miles distant,

Jan 1, 1886

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

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors' value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors' excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors' interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic'" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.'"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot's23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors' reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952

COMMITTEES. Iron and Steel. Albert Sauveur, Chairman. A. A. Stevenson, Vice-Chairman. Herbert M. Boylston, Secretary, Abbot Bldg., Harvard Sq., Cambridge, Mass. LOCAL COMMITTEES. Program Committee.-A. A. Stevenson, Chairman. Herbert A3. Boylston, J. E. Johnson, Jr., Henry D. Hibbard, E. Gybbon Spilsbury. Reception Committee.-J. R. Johnson, Jr., Chairman. Felix A. Vogel, William R. Walker. Dinner Committee.-E. Gybbon Spilsbury, Chairman. The opening session was held on Thursday morning, Oct. 16, 1913, at the Institute Headquarters in the Engineering Societies Building, 29 West 39th Street, New York, N. Y., and was called to order by President Rand, who addressed the meeting briefly before presenting Albert Sauveur, who responded to the President's address, and presided at the meeting. The following papers were then presented in oral abstract by their authors or authors' representatives: The Cleaning of Blast-Furnace Gas, by W. A. Forbes. Discussed by S. K. Varnes, H. N. Diehl, F. H. Wagner, Joseph Hartshorne, S. B. Marshall, J. W. Richards, J. E. Johnson, Jr., W. A. Forbes, and others.

Jan 12, 1913

By P. D. Merica, J. R. Freeman, R. G. Waltenberg

Contents Page Constitution of Commercial Aluminum.................. 4 Solubility of CuAl2 in Aluminum at Different Temperatures........ 9 Effect of Magnesium on Solubility of CuA12 in Aluminum ......... 15 Solubility of Mg4Al8 in Aluminum at Different Temperatures........ 15 Solubility of Metals and Metal Compounds in Aluminum.......... 20 Summary and Conclusions......................20 Aluminum and its alloys have been the subject of much investigation1 during recent years, in the course of which the principal features of the constitution of most of the binary alloy systems with aluminum have been determined. Except in the case of a few metals—silicon, bismuth, cadmium, lead, zinc, and tin—an aluminum-rich compound is formed in each binary system, which forms a eutectic with the aluminum or its solid solution with this compound: Thus such compounds as FeAla, CuA12, Mg4Al3, and NiAls are formed, which are found in aluminum-rich alloys of their respective series as eutectics with the aluminum solid solution. These compounds are, in all cases, hard and brittle and their presence affects profoundly the physical properties of the alloys in which they occur. Within the zinc-aluminum system a compound, Al2Zn,, is formed that decomposes at lower temperatures. Silicon and tin each form a simple eutectiferous series with aluminum; bismuth, lead, and cadmium are only partly miscible in the liquid state with it. The extent of the solubility in aluminum, in solid solution, of these compounds or of the elements themselves, in the case of those series in which compounds are not formed, is of the greatest importance in

Jan 1, 1921

By H. F. Gossenberger, J. J. Tietjen, J. J. Gannon, C. J. Nuese

External quantum efficiency measurements at 300" and 77°K are presented for vapor-grown GaAs and GaAs1-xPx electroluminescent diodes as a function of junction depth and doping. In GaAs, external efficiencies are found to decrease exponentially with increasing junction depth, defining an average absorption coefficient of 900 cm-1 at 300°K and 350 cm-1 at 77°Kfor epitaxial layers of p-type GaAs. It is shown that photon absorption losses dominate at room temperature and, in fact, account for most of the external efficiency degradation between 77° and 300°K. Healever, the internal ('junction) quantum efficiency is also found to decrease by a factor of 3.5 between 77" ALTHOUGH rapid progress has been made in recent years with GaAs, Gap, and their alloys for use in electroluminescent diodes, there are still important unknown factors related to the performance of these de- and 300°K. The dependence of GaAs efficiencies on donor and acceptor concentrations is presented, illustrating best efficiencies at donor concentrations of 1.5 to 2x 1018 cm-3 . External efficiencies are found to be independent of acceptor concentrations less than 3 x 1019 cm-3 but to degrade at higher doping. The fabrication of GaAsi-xPx electroluminescent diodes is briefly discussed. External efficiencies here for planar uncoated diodes are about 0.035 pct at 300°K and 0.4 pct at 77°for x = 0.42. A brightness of about 8500 ft-Lamberts is attained at 77°K and of 315 ft-Lamberts at 300° K. for curvent densities of 10 amp per sq cm. vices. For example, although the external efficiency is known to decrease by factors of typically 10 to 30 between 77°K and room temperature, the exact causes of this are still uncertain. Experimental results of ill' and carr2 with zinc-diffused electroluminescent diodes suggest that this external degradation is almost entirely due to increased absorption losses at room temperature, with a relatively temperature-independent internal efficiency; recent calculations by Gonda et al.3 corroborate this hypothesis. In contrast, Pilkuhn and Rupprecht4 find the internal efficiency of solution-grown GaAs laser diodes to degrade from 100 to 66 to 40 pct as the temperature is increased from

Jan 1, 1969

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.' Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner's treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1'2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By C. W. Spencer, J. Singer

A PARTIAL phase diagram for the As-Te system is given in Hansen.' The only compound reported is As2Te3, melting at 362°C. Stoichiometric quantities of reagent-grade elements were reacted in evacuated quartz and directionally cooled. The resulting ingot consisted of very thin threadlike crystals from which only very small single-crystal fragments were isolated. A powder diffraction diagram disclosed nonisomorphism with the analogous V-VI compounds insofar as these have been reported; Sb2S3, As2S3, Bi,S,, and Bi2Te3 data in the ASTM index of powder patterns, together with the single-crystal data on Sb2Se3,2 were used for the com- parison with the observed spacings. Single-crystal data confirmed the uniqueness of the As2Te3 structure. Single-crystal Weissenberg diagrams have so far yielded the following data: As2Te3 is monoclinic, space group C-m (OkO data still lacking), a = 14.4A, b = 4.05A, C = 9.92A, ß = 97". The cell volume is about 5802. The set of isomorphous ortho-rhombic cells of Sb2Se3, Sb2S3, and Bi2S, are apparently related to As,Te, in having one lattice constant close to 4.0 and with cell volumes as large as 540A8. Assuming Z = 4 for As2Te3 also, the density is calculated as 6.1 which agrees well with a roughly determined value of 6.0. A complete structure analysis is under way.

Jan 1, 1956

By R. P. Agarwala, M. S. Anand

Using residual activity technique, the diffusion of palladium, silver, cadmium, indium, and tin in alunzinum has been studied in the temperature range of 400" to 630°C. The diffusivities (in units of square centimeters per second) have been expressed as: IMPURITY diffusion in aluminum,1-9 silverand lead5 for cases of low solid solubility of the impurity in the host metal has yielded frequency factors in the range of l0-6 to l0-9 sq cm per sec whereas the activation energy is practically half the self-diffusion activation energy value. From the observed values of frequency factor, activation energy, and entropy of activation, it has been suggested' that these solutes are not diffusing by vacancy or interstitial mechanisms but by a mechanism which should be consistent with such low values of the diffusion parameters (Do and Q). However in spite of extensive work on these types of systems, the mechanism of diffusion is still not well understood. The present investigation on the diffusion of palladium, silver, cadmium, indium, and tin in aluminum has been carried out to throw further light on the diffusion mechanism in systems, where the solid solubility is very low (except for the case of silver). The results are discussed on the basis of solid solubility and the structural changes involved owing to the presence of the solutes in aluminum solid solution. An attempt has also been made to apply the existing theories of charge5-8 and size8 difference between the solute and the solvent. EXPERIMENTAL PROCEDURE Specimens (1/2 in. diam by 3/8 in. high) were machined out of pure aluminum (99.995 wt pct) rod obtained from Johnson Mattheys. They were sealed under vacuum in quartz tubes and annealed at 620° C for several hours; the grains thus developed were sufficiently large to eliminate the possibility of diffusion along the grain boundaries. The flat ends were prepared carefully after polishing as described previously,10 Radioactive nitrates of cadmium, indium, and tin and chloride of palladium containing, respectively, cd115, 1n114, sn113, and pd103 were dissolved in distilled water and mixed with 30 pct acetone. By means of a micropipet a drop of this solution was placed on a smoothly polished and lightly etched surface of the specimen. Due care was taken to see that the solution spread uniformly on the surface of specimen without trickling down its sides. Radioactive silver was elec-trodeposited using a AgCN-KCN bath. The amount of sample deposited in all the cases was not more than 0.1 µ thick. The samples were then sealed in quartz tubes in vacuum. The cadmium samples were sealed in a purified argon atmosphere to avoid evaporation. The samples were then diffusion-annealed. The temperature of annealing varied between 400° and 630°C and was controlled to ±5°C. On heating to -400°C,the deposits of cadmium, indium, and tin, which were of the order of 0.1 p in thickness, were converted to their respective oxides. The contribution of oxygen present in the lattice of aluminum due to these oxides has been calculated and found to be less than 10 ppm in all cases. Oxide method has already been used by other workers11'12 in diffusion studies without any controversy on the issue. However, in some of these investigations, metallic deposition was also tried. The diffusivities calculated from these measurements were found to agree very well with the diffusivities obtained by using the oxide method. Thus it is assumed that the measured diffusivities represent true diffusion coefficients. Since palladous chloride decomposes at about 500°C, the deposited samples which were to be diffusion-annealed below 500°C were heated in vacuum for a very short time at 500°C to allow the decomposition of palladous chloride to palladium metal. Time taken in decomposition of nitrates to oxides and chloride to metal was negligibly small as compared to the period of the diffusion anneals. The residual activity technique13 was used to study the diffusion profiles where thin layers from the specimen surface were removed by grinding it parallel to a flat surface on a 600-grade carborundum paper. The specimen was washed, dried, and weighed, the differ -ence of the weight being the measure of the thickness of the layer removed. After each such abrasion and weighing, the total residual activity on the surface of the specimens was measured by counting 0.656, 0.94,

Jan 1, 1968

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. . Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS.4 BRADLEY STOUGHTON.

Jan 10, 1913

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL .EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman 1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS, 4 BRADLEY STOUGHTON.

Jan 12, 1913

By N. Brown

IT has been observed that a hexagonal-close-packed crystal will undergo the same macroscopic displacements as an isotropic material if the basal plane is perpendicular to the axis of twist.&apos; Other orientations may produce both bending and twisting, but this analysis will be confined to pure torsion of a right circular cylinder. The z axis, the axis of twist, and the specimen axis are coincident. The displacements are given by Uq = rz, Ur = Uz = 0 [1] where 4 is the angle of twist per unit length. This requires rotational slip, as discussed by Frank&apos; and Wilman, which may be observed readily. The relative rotation of adjoining slip planes is simply produced by a movement of a planar grid of screw dislocations."." The screw dislocations are of the same sign and they move radially inward. For hexagonal-close-packed metals, the grid is hexagonal and the screw dislocations lie in the < 2110 > directions. The displacement of a point is the resultant of two displacements produced by intersecting screws sweeping over the point. The dislocations must pass over the point (r, o) in such a manner that its resultant displacement corresponds to the observed macroscopic displacement. If 6&apos; is measured from the [1010] direction, then for 0 < ? < ~/3, only the [1210] and 121101 type screw dislocations are needed to produce the required displacement. If n1 screws of type [1210] and n2 of type [2110] pass over a point, then, in order that Ur = 0 n, sin ? - n2 sin (/3 — 6&apos;) = 0. [2] If the tangential displacement is to be independent of 0, then n1 cos ? + n2cos (/3 —?) = N [3] where N is independent of ? and thus depends only on r. Nb is the tangential displacement where b is the Burgers vector. Since U? is a linear function of r, then N must be a linear function of r. If a2 is the outer radius and a, is the inner radius to which the plastic deformation has extended, then N = Nm2 r-a1 [4] This function meets the conditions that at

Jan 1, 1956

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP&apos; have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1940 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. TECHNICAL PUBLICATIONS in Classes A-Metal Mining, B-Milling and Concen-tration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETRO-LEUM TECHNOLOGY, which was issued quarterly in 1940 but will be issued every other month in 1941. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysical Methods of Exploration are issued as separate pamphlets. An Institute member is entitled to one copy of any TECHNICAL PUBLICATION or CONTRIBUTION. Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute accord-ing to their registration by classes. CONTRIBUTIONS and other TECHNICAL PUBLICA-TIONS will be sent upon request. A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page; minimum charge, 25¢. Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1.25 domestic, $1.35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2.50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7.80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers). MINING TECHNOLOGY, $6 per annum domestic, $6.60 foreign (metal mining, milling and concentration, Industrial Minerals Divi-sion, and mining geology papers.) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6.60 foreign. Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY is mailed each month. A member is entitled to one volume a year on his membership and he may purchase for $2.50 one copy of a volume not already received; additional copies of the same volume, $5. Nonmembers may pur-chase the volumes listed, at $5 each, plus 60 cents for Canadian or foreign postage. Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 50¢ each to members; to nonmembers 506 current issue and $1 each, back issues. Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4.00 foreign.

Jan 1, 1940

By W. A. Gibson, Zay Jeffries

It has been known for a number of years that certain aluminum alloys could be hardened by quenching from a temperature of about 500&apos; C. Immediately after quenching the total increase in hardness is not marked, but the hardness increases gradually so that after about 4 days, it has reached a maximum. The actual increase in hardness probably continues for weeks or even months, but in order to detect the differences after 4 days, it is necessary to make tests at rather long intervals. So far as is known to the authors, Alfred Wilm was the first to discover these properties in aluminum alloys.&apos; The aluminum-copper alloys are amenable to this treatment and the addition of magnesium makes the heat-treatment effect more pronounced. Until recently heat treatment of aluminum alloys has been confined to the worked alloys in the form of sheet or extruded products. The alloy that has been most used in this connection is known commercially as duralumin and has about the following composition: copper not exceeding, 6 per cent.; magnesium not exceeding, 2 per cent.; manganese not exceeding, 1 per cent.; commercial aluminum,2 balance. A typically good alloy in this range consists of: copper, 4 per cent.; magnesium, 0.5 per cent.; manganese, 1 per cent.; commercial aluminum, balance. This alloy can be rolled into sheets or extruded; and in this condition it can be heated in the ordinary furnace atmosphere to a temperature near 500° C. and quenched in water. After about 4 days it will have the following physical properties: tensile strength 55,000 to 60,000 1b. per sq. in. (3866 to 4218 kg. per sq. cm.); elongation in 2 in., 15 to 20 per cent. No harmful effects of the furnace gases or even the air, if the heating is effected in an electric furnace in an air atmospherc.

Jan 1, 1921

NEW MEMBERS The following list comprises the names of those-persons who became members during the month of January, 1914. Members ADIASSEWICH, ALEXANDER, Dept. of Commerce & Industry, 11, Nadejdinskaia, St. Petersburg, Russia. BEARD, JOHN W., Mine Supt., Lane-Rincon Mines, Inca, Temascaltepec, Mex., Mexico; BORCHERDT, WALTER 0., Supt The Bertha Mineral Co., Austinville, Va BREWSTER, BURT B., Sales Engr., Sullivan Machinery Co., 1127 Central National Bank Bldg., St. Louis, Mo: CHASE, ROGER E., JR., Assayer 3906 No. Baltimore St., Tacoma, Wash. CULBERT, J. VICTOR 7S4 Wellington St., London, Ont., Canada; DICKINSON, ALBERT W., Supt. Of Mines Bevier, MO. DODSON, T. M Mores, Colliery, Schuylkill Co., Pa FORREST, CHARLES N., Chem. Engr Maurer, N. J.

Jan 2, 1914

STANDING COMMITTEES. . Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, , ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR.., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 11, 1913

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult&apos;s law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa&apos;s4 data, and Kubaschewski7 has similarly treated Kawakami&apos;s7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By H. D. Strain

Potash is a generic term used to describe a number of compounds containing the element potassium (K), which is one of the three major plant nutrients. Potash content of these compounds is commonly expressed as percentage potassium oxide (K20), and the market value of the products is usually dependent on contained K20. Most of the potash produced (approximately 95%) is used in agriculture as fertilizer. Potash products today are shipped by producing countries all over the world to meet the need for increased food production. WORLD POTASH RESERVES Apparent world potash reserves are shown in Table 15.2B.1 and total some 96 billion mt of recoverable potassium oxide. The Canadian reserves account for approximately one-half the known world reserves. The reserves shown represent the potassium oxide content of a variety of potash-bearing ores. The major ore is sylvinite (a mechanical mixture of KC1 and NaCl) from which KC1 or sylvite is recovered (63.2% K20 equivalent). Other ores, such as langbeinite (potassium, magnesium sulfate-22.7% K20) and carnallite (potassuim magnesuim chloride-17.0% K20) are also mined in various parts of the world, mainly for the potassium content. Theoretically, potassium is available in almost unlimited qualities from brines and saline waters. To date, the cost of recovery from salt brines has been greater than the costs by mining operations, but new technology could make brines and seawater an increasingly important source. POTASH PRODUCTION Potash production dates back to the 1860s in Germany, which was the only recorded producing country until 1912. By 1912 Germany was producing approximately 1 million tpy of K2O equivalent. Production began in France in 1913 and in the United States in 1915. World potash production and consumption are shown in Table 15.2B.2 for the years 1950-51 through 1967-68. In 1967 and 1968 the major potash-pro¬ducing countries in order of importance were those listed in Table 15.2B.3. By 1972 Canadian production had outstripped U.S. production. WORLD CONSUMPTION World consumption of potash for the years 1950-51 through 1967-68 is shown in Table 15.2B.2. Table 15.2B.4 shows total world consumption of potassium materials in 1967-68 by country. More than 70% of the world&apos;s potash is

Jan 1, 1976