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By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By S. K. Tarby, W. O. Philbrook

Limited experimental data and a critical review of the literature are given to indicate that the true equilibrium distribution of manganese between carbon-saturated iron and blast-furnace type slags has not yet been satisfactorily established as a function of the composition, temperature, and pressure of the system. THE distribution of manganese between carbon-saturated iron and blast-furnace type slags has been studied by a number of investigators.1-7 Generalization of the results of these works indicates that the weight percent distribution ratio, (%Mno)/[%Mn], decreases with increasing temperature and slag basicity, in accord with thermodynamic data and practical observation. However, where comparisons among these studies can be made for similar slag compositions and temperatures, the reported values of the manganese distribution ratio are discordant. The variations are attributed to failure of the experimenters to bring their systems completely to equilibrium with graphite and CO at 1 atm, as judged by departures from silicon equilibrium. Even in the most recent work,5-7 this problem was recognized but the authors made the questionable assumption that equilibrium could prevail for manganese distribution even though other reactions were still in progress. Manganese equilibrium values for three particular slag compositions were required incidental to a kinetic study8 and were determined experimentally. Special pains were taken to approach concurrent equilibrium with respect to silicon. Although the results were not completely definitive, they indicate that the true manganese equilibrium distribution ratios are lower than have heretofore been reported. The data are presented together with a brief commentary on the literature to suggest the need for further work in this area. EXPERIMENTAL METHOD Equilibrium runs were carried out in a stationary, induction-heated graphite crucible closed by a graphite lid and flushed continuously by a slow flow of carbon monoxide at 1 atm pressure. Temperature was controlled manually within ±3 deg C with the aid of immersed thermocouples in mullite tubes protected against slag attack by graphite sleeves. The desired temperature was established by a calibrated Pt vs Pt-10 pct Rh thermocouple and control was then maintained using a more stable W-Mo couple. Runs were made at 1500º and 1575ºC for durations of 7.5 to 10.5 hr. The charges were calculated to yield 400 g of metal and 100 g of slag. The primary slag compositions and designation numbers were as follows:

Jan 1, 1963

By Elmer W. Pehrson

Minerals have played a prominent role in the affairs of man and nations since time immemorial but with the advent of the industrial revolution, expanding use of the products of the mineral kingdom became synonymous with the material progress of mankind. Individuals and business groups have recognized this fact so have been aggressive in searching for and utilizing mineral resources, with notable success. Indeed, their achievements are primarily responsible for the present Machine Age. On the other hand, until recently the body politic has failed to grasp fully the essentiality of minerals although, at times, access to mineral supplies has been an important factor in the political maneuvers of nations. This chapter is concerned primarily with the broader political and economic relationships of mineral resources to the world economy, and with the internal and external actions of nations in the field of minerals. Many factors that condition the mineral economy of regions and the world as a whole, influence the internal and external affairs of individual nations. The more important of these are: 1. The nature of man&apos;s dependence on minerals. 2. The problems resulting from the unique characteristics of mineral occurrence. 3. Geopolitical concepts. 4. Minerals and world power. Actions of individual nations affecting their mineral economy seek two basic objectives : 1. Attainment and maintenance of prosperity. 2. Military security. Other objectives may be cited but on careful analysis they become integral parts or extreme phases of the two points noted above. For example, the twentieth century aggressions of the USSR, Germany, Italy, and Japan might be considered as direct bids for world power but they also can be interpreted as exaggerated or mistaken efforts toward military security and peacetime prosperity. Similarly, trade barriers, nationalization of industries, foreign exchange manipulations, taxation, monopolistic prac-

Jan 1, 1959

By J. B. Hess, C. S. Barrett

TO reach equilibrium between different phases in cobalt-rich alloys requires prohibitively long annealing cobalt-richalloystimes when temperatures are below about 700°C. The fact that a transformation from face-centered cubic to close-packed hexagonal readily tered takes place at temperatures below this in the cobalt-rich solid solutions is not an indication that thermally activated processes occur at an appreciable rate, for the transformation is well established as martensitic in nature. Wide divergence between heating and cooling experiments and high sensitivity to prior heat treatment make it difficult to judge temperatures of equilibrium between the phases.&apos; One object of the present work was to see if the information object of on the relative stability of phases could be gained by substituting plastic deformation for thermal agitation. Procedures were worked out that led to the determination of a diffusionless type of phase diagram, which represents the temperature of of phase equal stability for phases of the same composition, and the technique was applied to the Co-Ni system. Another object of the work was to see whether or not deformation would generate frequent stacking faults when these were thin lamellae of quentstackingfaultsa phase having higher free energy than the parent phase. The alloys were prepared in 80 to 100 g melts from cobalt (with metallic impurities estimated spectrochemically as follows: Ni, 0.05 pct; Fe, 0.001 pct.; Mg, Si, Cu, Cr, Al, < 0.001 pct) and Mond Car-bony1 nickel (with Fe, 0.05 pct; Si, 0.003 pct; C, 0.61 pct.; Cu, 0.001 pct; Co, Cr not detected, < 0.01 pct). The metals were melted in pure Al2O3 crucibles. An atmosphere of argon, that had been purified by passing over hot magnesium chips, was used for the alloys that, by analysis of the portions of the ingots actually used, were found to contain 15.3, 25.7, and 35.0 pct Ni, and vacuum melting (after degassing) was used for those containing 29.4 and 31.5 pct Ni. After induction melting the alloys were allowed to solidify in the crucible, and slices % in. thick x ½ in. in diam were annealed 12 hr at 1350°C for homogenization. These same specimens were used throughout the series of experiments, with annealing treatments of 4 hr at 900°C in purified hydrogen followed by furnace cooling, alternating with the deformation and X-ray tests discussed below. Results Spontaneous transformation was observed on cooling to room temperature in all alloys containing 29.4 pct Ni or less and by cooling the 31.5 pct alloy to — 195°C but was not observed in the 35 pct alloys after cooling to —195°C. These results are in satisfactory agreement with the cooling experiments of Masimoto.4 From these data it is clear that the temperature of beginning transformation M,,, drops to 20°C with the addition of about 30 pct Ni. The test for spontaneous transformation was metallographic. Specimens were thermally polished by annealing 10 hr in hydrogen at 1350°C, then furnace cooled; if trans- formation had occurred there were relief effects visible on the thermally polished surfaces. These markings were narrow straight lines, usually resolvable at high magnification as clusters of fine lines that resembled slip lines. It was concluded that they resulted from displacements on (111) planes, for the number of directions in individual grains often reached but never exceeded four, and lines could always be found parallel to the thermally etched (111) boundaries of annealing twins. The markings were thus consistent with the idea that the transformation occurs by (111) plane displacements (Shockley partial dislocations moving on (111) planes). This was further confirmed by X-ray tests for stacking disorders. Using an oscillating crystal technique previously employed to detect strain-induced faulting in Cu-Si alloys," streaks indicative of the stacking faults were looked for and found on X-ray films of the spontaneously transformed 25.7 pct Ni alloys, as expected by analogy with Edwards and Lipson&apos;s results on pure cobalt." The streaks were much intensified after rolling at room temperature. Transformation induced by plastic strain was investigated as a function of alloy composition and temperature of deformation. A series of tests was made to determine suitable straining and X-raying techniques. Filing was found inferior to abrasion in converting cubic samples to hexagonal, and abrasion was less effective than peening in producing smooth unspotty Debye rings in the X-ray patterns. Because the diffraction lines were broad, Geiger-counter spectrometer records of filings were less sensitive in revealing small amounts of transformed material than X-ray patterns recorded on films in a small diameter camera. After these exploratory tests the following methods were adopted. Specimens that had been annealed at least 4 hr at 900°C and furnace cooled were mounted in a block of aluminum, brought to temperature, and peened thoroughly with a mullite pestle preheated to the same temperature. The specimens were then quenched to room temperature. In peening, a circular area of % in. diam was given 500 blows. A few control tests showed that an additional 1000 blows did not detectably change the proportions of the phases present. The amount of transformation was judged by X-ray reflection patterns from the peened surface, using the innermost four lines of the cubic and the hexagonal patterns with filtered CoKa radiation,

Jan 1, 1953

A group of prominent engineers and contractors of Chicago and vicinity have cooperated in forming a Joint Committee on Military Engineering. The founders are members of all of the leading engineering and contracting organizations of Chicago, including the local branches of the national engineering societies. The purposes of the Committee are to further military preparedness among engineers, contractors and their associates by the following means: (1) Courses of lectures; (2) assigned reading; (3) studies and practical instruction in military engineering;. (4) assisting engineers to qualify as officers in the National Reserve Corps of Civilian Engineers; (5) urging enlistment in and support for engineer troops of the National Guard and such other organizations as the Government may create; (6) furthering instruction in military engineering in training camps and the attendance in them of those qualified; (7) by such other means as from time to time may be deemed advisable. The Joint Committee has already prepared a program covering the vital points outlined. To date the program is practically complete for a period extending from April 20 to July 25. Something of interest will be taken up each week, including lectures by Lieutenant-Colonel W. B. Judson, Engineer Corps, U. S. Army; two lectures by Major P. S. Bond, Engineer Corps, U. S. Army; Lieutenant-Colonel Mason M. Patrick, Engineer Corps, U. S. Army, and several exhibition drills, terrain exercises and inspection trips under the direction and guidance of various officers of the Engineer Troops of the Illinois National Guard. Additions to the program will be made from time to time. &apos;

Jan 5, 1916

By T. A. Read, H. K. Birnbaum

Deformation of AuCd alloys having the 8 (orthorhombic) and (3" (tetragonal) structures occurs by the stress induced motion of twin boutdaries. A restoring force acts on displaced twin boutdaries as a result of internal energy increases in the volume through which the boundaries are displaced. The phenomonology of the twin boundary motion is described and a mechanism for twin boundary motion and the restoring force is proposed. A time-dependent stabilization behavior of the twin boundaries, which is observed after the twins are formed by the diffusionless phase transformations, is described. THE AuCd 8 phase (ordered bcc structure) exhibits a transformation to a phase having an orthorhombic structure, 8&apos; (space group D&apos;), for compositions in the vicinity of 47.5 at. pct Cd and to a phase having a tetragonal structure, 8" (point group 4/m, m,m), for compositions in the vicinity 50.0 at. pct Cd. Both transformations are diffusionless, occur on cooling at 60" and 30OC, respectively, and are crystallo-graphically reversible.&apos; They are accompanied by an inhomogeneous deformation which was observed to be twinning in the low-temperature phase. 3&apos;4 The transformations may occur by a "single interface" or by "multiple interfaces."5&apos;6 In the "single interface" transformation, the twinned product phase consisted of two twin orientations as shown in Fig. 1. In the multiple interface transformation the product phase contained "domains" each of which contained two twin orientations, Fig. 2. Deformation of specimens containing transformation twins was achieved by motion of the twin boundaries. Releasing the applied stress resulted in the displaced twin boundaries returning towards their initial positions. This "pseudo-elastic" behavior of the boundaries varied with time after the formation of the twin boundaries by the transformation.

Jan 1, 1961

By Charles S. Barrett, F. W. Steadman

DEFORMATION bands of surprising regularity are found in large-grained polycrystalline copper after cold-rolling (Fig. I). Individual bands frequently are large enough to permit a determination of their orientation by means of etch pits and an optical goniometer. Measurements have been made on 21 areas in seven different grains, and these, combined with X-ray studies of nine single crystals that had been cold-rolled after mounting in a polycrystal-line block, have contributed to a better understanding of the preferred orientations in rolled copper just as similar studies have for rolled iron&apos; and brass.2.3 Particular attention was given to determining orientations that are stable during rolling and to the manner of fragmentation and rotation of unstable grains. The possible role of twinning was also carefully investigated. The texture of polycrystalline copper after cold-rolling is well established by the pole figures that have been plotted by Schmid and Staffelbach,4 Iweronowa and Schdanow,5 and Brick and Williamson,3 all of which are in substantial agreement. There has been some divergence in the list of individual "ideal" orientations that have been used to describe the texture by these observers and others,6 although the orientation (110) [112]-that is, (110) parallel to the rolling plane and [112] parallel to the rolling direction-is generally recognized as the most prominent orientation and (I12) [111] one of the lesser orientations. Other orientations have been given by some observers as (236) [533], (100) [001], and (I 10) [001]. The texture of copper has also been described as (135) [533].6.1 The sum of these orientations provides a reasonable approximation to the complete pole figure, but it does not follow that these specific orientations are necessarily of fundamental significance, for the choice of indices is arbitrary, within limits. Furthermore, a detailed investigation of the ideal orientations in cold-rolled iron discloses continuous ranges of equally favored positions rather than definite positions of high stability,1 and similarly Brick&apos;s observations in a single crystal of a brass2 suggest that all orientations in the range between (110) [113] and (110) [117] are about equally stable. MATERIALS AND METHODS The material used was vacuum-cast electrolytic copper kindly supplied by L. L. Wyman, of the General Electric Co.* Slices 1/2 in. thick and 2 1/2 in. square, cut from the ingot, were rolled with 50 per cent reduction per pass to final thicknesses between 0.02 and 0.04 in., and etched to develop cube-face etch pits suitable for goniometric work.8 The etch was light on some strips and deep in others.

Jan 1, 1942

B. R. Coil (Electrical Installations at the Miami Mine are Cheaper with Flexible Cable, P. 356) was born in Higginsville, Mo., and attended McKinley High School and Missouri School of Mines. He received a B.S. in mining engineering. Mr. Coil has worked for the Braden Copper Co., Rancagua, Chile as junior engineer and foreman. He was employed by Miami Copper Co. as a jigger boss, shift boss, development engineer and mine foreman. He worked as mine superintendent and general superintendent of the Castle Dome Copper Company, Inc. Mr. Coil may be reached at Box 100, Miami, Ariz. He is an AIME Member. Mr. C. R. Ross was co-author with Mr. Coil in the preparation of this paper. His paper covers the present installation of electrical equipment in block caving stopes along with background data. In this paper he has given one solution to wiring problems in heavy stopes.

Jan 1, 1952

By R. E. Ogilvie, N. L. Peterson

Intevdiffusion and intrinsic diffusiorz coefficients were determined in the uranium-niobium system from diffusion couples analyzed with an electron microbeam probe. A Previously unveported intermediate phase, designated in this report as the delta phase, was found to exist along the mobium-rich side of the miscibility gap. Its composition width was determined from the concentration gradients in the diffusion couples. The presence of this phase was also confirmed by microhardness analysis and metallographic observations. THE excellent corrosion resistant properties, high-temperature strength and reasonable nuclear properties of niobium have prompted its use as an alloying element with uranium and as a possible cladding material for reactor fuel elements. Hence the formation and growth of intermetallic phases as well as diffusion data for the uranium-niobium system are of considerable practical importance to metallurgists and nuclear engineers. Diffusion zones may exhibit varying degrees of complexity dependi.ng upon the mutual solubility of the metals involved, and the intermediate phases which may form. In the simplest case where the metals exhibit a calmplete range of solid solubility, a single phase region is produced. Generally, however, the metals may react to produce a multiphase diffusion zone containing several layers of intermetallic phases. A number of investigatorsl-6 have analyzed the concentration gradients present in diffusion couples in order to investigate phase equilibria and solu- bility limits. If diffusion is the rate-controlling process in establishing a concentration gradient, the compositions at the interfaces of the intermediate phases will represent the equilibrium values expected from the phase diagram at the temperature at which diffusion has taken place. No published information is available at this time on diffusion in the uranium-niobium system. A number of investigators7-" have contributed information to the construction of the uranium-niobium phase diagram from other than diffusion techniques. There is good agreement on the high uranium side of the phase diagram, but the high niobium side of the miscibility gap still remains somewhat in doubt. The phase diagram as determined by B. A. Rogers, et al.7 is shown in Fig. 1. The present work was aimed at obtaining fundamental information about the solubility limits of the miscibility gap and diffusion in the uranium-niobium system. A Kirkendall effect, which might be expected on the basis of the rather large difference in melting points between uranium (1132°C) and niobium (2415" C), was also investigated. The concentration gradients were measured by an electron microbeam probe technique, similar to that used by Castaing,l2 Adda and philibert,13, l4 and Macres.4

Jan 1, 1961

By L. F. Stutzman, George Thodos

The friction factor plot presented by Cornell and Katz4 and developed for the flow of fluids through consolidated formations has been directly adapted for handling fluid flow problems involvitrg both linear and radial flow. In this adaptation the friction factor plot is used directly for the solution of problems and thereby eliminates the use of conventional equations which are specific to laminar (Darcy) or turbutent flow. This upproach overcomes the disadvantages inherent in the use of these conventional equations. It eliminates the necessity of checking the type of flow occurring in order to identify the specific equation which must be used. In radial flow problems, because of the increasing mass velocity of the fluids as they approach the wellbore. the type of flow may no longer remain laminar. Consequently, it is necessary to use more than one equation in a problem and to identify the range over which each equation should be applied. Finally, in practice it has been found that much of the flow of gases through consolidated media occurs in a range that is neither laminar or turbulent. For this transitional region, no convenient equations are available. The method and presented friction factor plot are appficahle to both liquids and gases. INTRODUCTION The flow of fluids through unconsolidated media in packed beds has been treated extensively by a number of investigatorsl,2,3,5,7,8 Most of these studies present friction factors as a function of modified Reynolds number similar to those developed for conventional fluid flow through pipes. These friction factor plots are presented for linear flow; however, Elenbaas and Katz have extended these concepts to apply to radial flow. All of these studies on unconsolidated materials require a knowledge of packing properties such as sphericity. porosity, and particle diameter. Sphericity and particle diameter cannot be defined at the present time for consolidated formations such as those commonly found in gas or oil reservoirs. As a result many investigators have not utilized friction factors and Reynolds number in the study of fluid flow through consolidated media. However, Cornell and Katz4 present a plot (Fig. 1) for the flow of fluids through consolidated porous media, in which the friction factor defined as: The turbulence coefficient, P, is related to the formation permeability, K, as presented in Fig. 2. Three different types of flow may exist in the flow ot

Jan 1, 1957

By J. S. Browning

The pegmatites of the Kings Mountain-Lincolnton, N. C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li2O (lithia) as spodumene.1 The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2,3,4,5,6,7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals.

Jan 7, 1961

Elected Died 1895 ABBOTT, AI ATTHUR 1908 1882 ABBOTT, ARTHUR V 1906 1905 ABE, MASAYOSHI 1909 1903 ADAMS, CHARLES C. 1905 1906 ADAMS, JOHN C. 1913 1905 ADAMS, WILLAMS 1909 1903 ADAMS, W. EDWARDS 1910 1884 ADDY, MATTHEW 1896 1906 AFFLECK, WILLIAM A. 1911 1889 AKERS, WILLIAMS A. 1906 1905 ALABASTER, RUPPERT C. 1911 1899 ALBERGER, LOUIS R. 1911 1894 ALLEN R B 1896 1905 ALLEN, R. SCOTT 1906 1886 ALLISON, ROBERT 1916 1874 AMIOT, H. 1892 1886 AMSLER, CARL 1894 1898 ANDRSON, JOHN W 1905 1895 ÅNGSTROM, CARL 1901 1887 ARCHBALD, JAMES 1910 1900 ARLETT, GEORGE H 1906 1895 ARMSTRONG, JOHN F 1898 1882 ARNOLDS, HUGO 1886 1875 ASHBURNER, CHARLES A 1889 1872 ASIIBURNER, WILLIAM 1887 1883 ATKINS, C M , JR 1885

Jan 1, 1917

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1903 * ADAMS, CHARLES C. 1905 1905 * ADAMS, WILLAMS 1909 1884 *ADDY, MATTHEW 1896 1889 * AKERS, WILLIAMS 1906 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 *AMIOT, H 1892 1886 *AMSLER, CARL 1894 1895 *ÅNGSTROM, CARL 1901 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUSTEN, PETER T 1907

Jan 1, 1910

By C. J. Beevers

Tlze influence of zirconium hydride precipitate mprphology on the fructure of Zr-H alloys tested at strain rates of 10- sec at 20° and - 196°C and at strain rates of -500 sec.-1 at 20°C has been inves-tigated. The critical stage in the embrittlement of these alloys was the fracture of the zirconium hyhide precipitates to form large interval cracks at a stress of 25,000 10 137,000 psi. In specimens con-temping up to 100 ppm H the preciptates existed as isolafed platelets in the zirconium matrix and their fracture as enhanced by low temperature (—196°C) and high strain rate (-500 set-f) loading. These resl~lts lead to the conclusion that the rate of strain hardening of the zirconium metal controls the frac-tzrm of the hydride platelets. Increased hydrogen contents of 500 to 2000 ppm resulted in an increase in the 1)volume fraction and size of precipitates and crlso led to crack propogation in the hydride at both 20 and —196C at the low strain rates (10&apos;* sec-&apos;). Quenching led to refinerment of hydride precipitate size and reduced the degree of embrittlement at — 196°C; this effect is attributed to the absence of fracture of the fine precipitates. The formation of zirconium hydride precipitates has been shown to be the cause of hydrogen embrittlement of zirconium.&apos; Several investigators&apos;-" have studied the problem in broad outline, demonstrating that impact-loading conditions, testing temperatures below room temperature, and increasing hydrogen content produce increased brittleness. For example, Muehlenkamp and schwope2 showed that the transition temperature for notched impact tests was raised from 150" to 350°C on increasing the hydrogen content from 45 to 490 ppm. The degree of embrittlement is also controlled by the morphology of the zirconium hydride precipitates. The solubility of hydrogen in zirconium decreases from 600 ppm at 550°C to 10 ppm at 20"C,~ so that the form of the zirconium hydride precipitates (ZrH2) can be modified by varying the cooling rate through the Zr-aZr + ZrH2 phase boundary.= Forscher showed that quenching a specimen containing 35 ppm H from above 315°C resulted in a reduction in area of 70 pct at -196"C, whereas slowly cooling from above 315°C resulted in a ductility of half this value. The role of the hydride precipitate in the fracture process has been examined by Young and schwartz6 and more recently by westlake.&apos; From metallo-graphic observations on slowly cooled Zr-H alloys they have suggested that cracks are nucleated in the hydride precipitates by the interactions of twins in the zirconium metal with the hydride. The experiments reported in this paper show that crack propagation in the zirconium hydride precipitates is the critical stage in the embrittlement of Zr-H alloys. The factors influencing fracture of the hydride precipitates and crack propagation in the zirconium metal will be related to the problem of embrittlement. EXPERIMENTAL TECHNIQUES The zirconium used in these experiments was produced from an ingot of vacuum arc-melted iodide zirconium forged down to 1 in. diameter at 800&apos; to 850°C. The 1-in.-diameter bar was surface-machined and cold-swaged to 0.375 in. diameter. After a vacuum anneal at 800°C for 1 hr the hardness was 60 to 70 Vdh. The total impurity content was approxi-

Jan 1, 1965

By A. W. Fahrenwald

Flotation practice in Idaho is now about 13 years old. The advance has been steady during these 113 years. The operators have been alert to take advantage of the newest developments and they have themselves made a constant effort to improve their work. The metallurgical improvements are due to the development of (1) better equipment, (2) better reagents, and (3) better understanding and control of the process. During the eight years the writer has been in this district, there has been continuous experimentation by several companies to improve the ore dressing by flotation methods. Gravity concentration has fought hard to hold its place, and although it is true that gravity processes have been improved during this period, nevertheless, in several of the important mills of the district the few tables that managed to hang on have finally given way. On the straight-lead ores, tables and jigs are still used; and, due to better classification, their hold on this job has been strengthened. Ores of the District The ores of the district are of two general classes: (1) clean lead ores, such as those from the Bunker Hill and Hecla mines, and (2) complex lead-zinc ores. The general impression prevails that the clean lead ores, class 1, are simple and that it is easy to obtain high recoveries and good grade products. This, in a way, is a false impression; there is quite a high percentage of locked middling in these ores at 100 and&apos; 150-mesh sizes. Improved classification preparatory to table treatment of this type of ore has made it possible to segregate effectively a high-grade middling which is further comminuted and floated. The complex lead-zinc ores of the district, of which the ore from the Morning mine of the Federal Mining & Smelting Co. is a typical example, always have presented a difficult problem. It always has been comparatively easy to make a clean lead concentrate, but it never has been possible to concentrate sphalerite with a specific gravity of 4.10 from siderite of gravity 3.88. Also, a large percentage of the galena and sphalerite of this class of ore refuses to separate out until the crushing has been carried

Jan 1, 1928

By K. A. Johnson, F. H. Ellinger, C. C. Land

The Pu-In phase diagram has been determined by thevmal, filtvation, micrographic, and X-ray diffraction methods. This alloy system is characterized by 1) limited solubility of indium (-2 at. pet) in 6 and e plutonium, 2) one eutectic, and 3) fizte intermediate phases. Of the latter, PuIn and PuIn3 melt con-gruently, and Pu31n, Pu31n5, and the high-temperatuve 7 solid solution are formed peritectically. The n phase decomposes eutectoidally into Pu3In and PuIn at 865°C. Although the 6 phase can readily be retained to room temperature, it is not thermo-dynamically stable below 300°C. The Pu-In system has been investigated at Los Alamos as part of a study of the alloys of plutonium with the group 111-B elements. Constitutional studies of the Pu-A1 and Pu-Ga systems have been reported earlier.&apos;9&apos; To date, published information on the constitution of Pu-In alloys covers only the identification of the intermediate phases Pu3In and PuIn3.3,4 EXPERIMENTAL The alloys were prepared from five different lots of plutonium and three different lots of indium. The principal impurities in the plutonium differed from lot to lot within the following limits (in ppm): iron, 30 to 80; nickel, 30 to 60; aluminum, 15 to 30; silicon, 20 to 145: thorium, 50 to 300; carbon, 75 to 335; and oxygen, 20 to 135. Spectroanalysis of the indium showed that two of the lots were 99.9 wt pct pure, and the third was 99.98 wt pct pure. The alloys, in the form of about 5-g buttons, were prepared by arc melting in conventional equipment. The components for each alloy were weighed to the nearest 0.1 mg. In most instances the weight losses during melting were negligible; therefore confirmatory chemical analyses were usually not made. A few results are given in Table I. Density measurements of the arc-cast buttons were made by the liquid displacement of bromoben-zene. Heat treating was done in muffle furnaces controlled to +2°C. The alloy buttons were wrapped in tantalum foil before being enclosed in evacuated clear silica capsules. As a precaution against breakage, each capsule was in turn placed in a silica tube closed with a refractory wool plug prior to being charged into the furnace. For a moderately fast quench of the alloys, the outer protection tubes containing the capsules were plunged into cold water. Differential thermal analyses (DTA) in racuo were performed at heating and cooling rates of about 1.5°C per min. Tantalum crucibles having inverted thermocouple wells were used for most of the analyses. It was found micrographically, however, that the liquid alloys containing more than about 35 at. pct In reacted with the tantalum, resulting in contamination of the surface of the alloy. A search for a more satisfactory crucible material was not successful: tungsten and yttria behaved comparably to tantalum; thoria, vitrified magnesia, and vitrified alumina severely contaminated the alloys. So as to minimize the contamination by the crucible mater-

Jan 1, 1965

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1905 * ABE, MASAYOSHI 1909 1903 * ADAMS, CHARLES C. 1905 1906 * ADAMS, JOHN C. 1913 1905 * ADAMS, WILLAMS 1909 1903 * ADAMS, W. EDWARDS 1910 1884 *ADDY, MATTHEW 1896 1906 * AFFLECK, WILLIAM A. 1911 1889 * AKERS, WILLIAMS 1906 1905 * ALABASTER, RUPPERT C. 1911 1899 * ALBERGER, LOUIS R. 1911 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 * AMIOT, H. 1892 1886 *AMSLER, CARL 1894 1898 ** ANDRSON, JOHN W 1905 1895 *ÅNGSTROM, CARL 1901 1887 * ARCHBALD, JAMES 1910 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUSTEN, PETER T 1907

Jan 1, 1917

By GEORGE ROBERT DE BEQUE

WHAT is wrong with oil shale? The answer is of interest to the public, to the oil refiner, and to the engineer. Many people have invested in shale land or shale securities, and others would invest if early development of the industry were certain. In the face of increasing demands for oil products, oil refiners are threatened with inability to maintain present output unless the supply of domestic petroleum is supplemented. Development of the oil shale industry would open a new field for engineering services. The object of this paper is to suggest reasons why there is but one shale plant in operation in the United States, and to discuss the probable time when the business will be firmly established in Colorado. As the Colorado deposits are the richest and largest in the world, ample supply of material is assured, consequently, this discussion will be confined principally to technical problems and economic problems affecting shale development.

Jan 1, 1924

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757&apos; and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick &apos;needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,&apos; are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed&apos; by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke&apos;s law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By R. Wang, N. J. Grant, B. C. Giessen

By crystallographic and X-ray methods, the existence and isonzorphism of Ti3Rh5 and Hf3Rhs were confirmed. Both phases are of the orthorhombic Ge3Rh5 type; lattice parameters and refined positional parameters are given. The structure is related both to the filled-up NiAs-B8 and Cu-AI types. An analogous phase with zirconium does not exist; the effect of ternary substitutions for titanium ad hafnium suggests a size factor limit to be active. A recent survey of phase diagrams of the T4 metals titanium, zirconium, and hafnium with the T, noble metals rhodium and iridium indicated the existence of the A3B5 phases Ti3Rhs, ZrsRhs, and HfsRhs. Ti3Rhs and Hf3Rh5 were found to be isostructural, based on the line-rich powder patterns which had not been analyzed. Zr3Rh5 was considered to have a substructure of the NbRu type (orthorhombically distorted B2-CsCl type).&apos; Because, in combinations with other transition metals, hafnium and zirconium are generally more likely to form isostructural phases than hafnium and titanium (with the significant exception of the Ti2Ni-"E93" type phases based on T4 metals2), the reversal of this relation for the A3B5 phases was of interest. As shown in the following, the nonexistence of Zr3Rhs has been established, the structures of Ti3Rh5 and Hf3Rh5 have been worked out, and crystal chemical relationships and stability criteria are reported. EXPERIMENTAL METHODS AND RESULTS Alloy Preparation and Phase Diagram Work. Alloys were prepared from high-purity (99.99+ pct) elements by arc-meltin3,4.Heat-treated alloys were annealed in a vacuum of 3 x X torr for 24 hr at 1300DC. Metal-lographic samples were etched electrolytically in concentrated HCl with 5 v ac for 5 min.3 X-ray diffraction powder patterns were taken on a GE XRD-5 dif-fractometer with Cum radiation at low scanning rates (0.2 deg per min for 28). It was confirmed that Ti3Rhs and Hf3Rh5 have similar diffraction patterns, and that an alloy with the composition Zr3Rhs has a different pattern. Six Zr-Fh alloys with 59 to 69 at. pct Rh were therefore prepared and investigated in the as-cast state by X-ray diffraction and metallography. Alloys at 59 and 61 at. pct Rh were found to be a single phase, with the distorted B2-CsC1 type structure typical for the off-stoichio- metric region of the phase (Zr,-,Rh,)Rh. This phase forms a eutectic with ZrRhs at about 66 at. pct Rh: accordingly, alloys between 61 and 69 pct at. pct Rh consisted of two phases. There is no evidence for the existence of Zr3Rh5. Based on the results in Rafs. 1 and 5, on the present work on Zr-Rh, and on several additional alloys investigated, the portions between the AB and AB3 stoi-chiometry for Ti-Rh, Zr-Rh, and Hf-Rh are as follows: Further, several ternary alloys near Ti3Rhs and Hf,Rhs were prepared in which it was attempted to replace titanium and hafnium partly by zirconium, niobium, tantalum, and germanium. The results will be discussed in a later section. Structure Determination of Ti3Rh5. Since Ti3Rh5 and Hf3Rh5 are isostructural, the following discussion will largely deal with the former. Although the powder pattern of TisRhs is complex, as found previously,1 it could be indexed by comparison with other structures of A3Bs stoichiometry. Ti3Rh5 was found to be isostructural with Ge3Rh5, whose orthorhombic structure had been elucidated by Geller.9 As both the sizes and atomic numbers of germanium and titanium are comparable, the unit cell volume and the peak intensities could be expected to be similar; however, significant differences exist in the atomic positions, as will be shown. All lines in the powder patterns of Ti3Rh5 and Hf3Rhj could be indexed with primitive orthorhombic unit cells with the lattice constants: The fractional errors are 10 The low-angle portion of the indexed powder pattern of Ti3Rh with sin2 8 < 0.30 is listed in Table I. The extinction laws Okl only with k = 2n and hOl only with h - 2n are compatible with the space group Pbo2 and the more symmetrical space group Phnm of Ge3Rh5. Finally, the positional parameters of Ti3Rh5 and HfsRhs were refined under the assumption that titanium and hafnium occupy the germanium positions in Ge3Rh5. Integrated intensities were obtained from the diffraction patterns by planimetry. Intensities of overlapping reflections were separated by an iteration process incorporated into the least-squares positional refinement program according to a method described previously. The intensities of Ge3Rh5 were used in the first separation cycle, while the atomic parameters of Ge3Rh5 were used as starting values in the first refinement cycle. Absorption due to specimen

Jan 1, 1970