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By B. A. Wilcox, A. H. Clauer

DURING the course of an investigation on the high-temperature creep behavior of TD Nickel* (Ni + 2) vol pct ThO2), it was observed that the creep fractures were similar in appearance to low-temperature ductile fibrous fractures and creep ruptures by cavitation. Microfractographs of fibrous ruptures are typically characterized by a dimpled appearance, with second-phase particles frequently found near the bottom of the dimples.'-4 These somewhat resemble creep ruptures by cavitation, in that fracture occurs by void formation, with the subsequent growth and final merging of the voids to form a complete fracture.' It is the purpose of this communication to describe the creep fracture of TD nickel and suggest a mechanism for the rupturing process. The discussion is relevant to material crept to fracture in vacuo at a constant stress of 18,000 psi, over the temperature range 900" to ll00°C. The material used in this investigation was 1/2-in.-diam bar stock supplied by Du Pont, contain- ing 2.3 vol pct Tho2. The final fabrication treatment consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fibered structure with a transverse grain size of -1 µ and a longitudinal grain size of 10 to 15 µ. Selected-area diffraction indicated that the fiber axis was parallel to (00l), in agreement with the results of Inman et a1.6 The thoria particle size varied from 80 to 1000Å, with an average size of 400Å, and the mean particle spacing was about 1200Å. The remarkable structural stability7 was confirmed by annealing for 6 hr at 1300°C (about ' 0.9 the absolute melting point). Transmission electron microscopy revealed that the only structural change was a slight decrease in dislocation density. Furthermore, recrystallization or grain growth during creep has not been observed. All specimens were annealed in vacuo at 1300°C for 3 hr prior to creep testing. The following times to rupture were obtained for vacuum creep tests at a constant stress of 18,000 psi: 900°C, 854 hr; 930°C,

Jan 1, 1965

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By Sydney H. Ball

I. INTRODUCTION. DURING the past 50 years the attention of mining-men has been turned to Africa, and within the past decade prospecting-expeditions sent into Central Africa have resulted in the opening-up of several mines. Having recently spent two years in the Belgian Congo for the Société Internationale Forestiere et Miniere du Congo, it is our purpose to outline briefly the mining-conditions in that part of Central Africa. Before it became, in 1908, a Belgian colony, this region was known as the Congo Free State. II. LOCATION AND AREA. The Belgian Congo lies in southwestern Central Africa, west of the continental divide, is illustrated in Fig. 1. It has a coastline of but 20 miles on the Atlantic, but widens rapidly eastward to points 5° north and 14° south of the equator. Its area is 908,000 sq. miles, which is almost one-quarter that of the United States and Alaska, or more than one and one-half times that of Alaska. Stated in other terms, its area is nearly one-third that of the United States, exclusive of Alaska and the insular possessions, or more than that of all the United States east of the Mississippi river. III. TOPOGRAPHY AND DRAINAGE. From north to south, Africa is made up of three topographic elements: 1, the Atlas mountains, a highly-accentuated region

Apr 1, 1910

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers'-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-' and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

By W. A. Anderson

IN the pressure die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger and a complete shutdown of the equipment. All of the zinc alloys used for pressure die-casting today contain approximately 4 per cent of aluminum, which is more than sufficient to make plunger operation feasible. The clearance between the plunger and its bushing is an important matter. As the space becomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still used in some machines. However, the rate at which the plunger clearance increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new materials more capable of retaining the desired clearance during long periods of use. Today many die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the plunger will operate for a long time, of course. The authors have developed a laboratory apparatus in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clear-ance area.

Jan 1, 1939

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By H. J. Engell, W. Frank, A. Seeger

SWISHER and ~urkdogan' have determined the solubility of oxygen in a iron. They found it to lie between 7 and 10.5 at.-ppm at 881°C. Using earlier work on the permeability of oxygen in bcc iron,' they arrived at the following expression for the diffusion coefficient of oxygen in bcc iron (k = Boltzmann's constant, T = absolute temperature): where The present authors3 have estimated the activation energy QD for the diffusion of oxygen in bcc iron in two different ways from various experimental data.2'4"6 In the first method QD + QS (QS = heat of solution for oxygen in bcc iron in thermodynamic equilibrium with solid FeO) was determined either from data on the reduction of FeO with hydrogen4 or from measurements of the internal oxidation of silicon in a iron.5 Using an estimate of QS from investigations of the oxygen solubility in 6 iron2 (in thermodynamic equilibrium with molten FeO) Q = 0.97 ev or Q~ = 1.06 ev were obtained. From the magnitude of these values it was concluded that oxygen migrates interstitially in bcc iron and that consequently the activation energy QD for diffusion of oxygen has to be identified with the migration energy E~ of the oxygen atoms. Therefore, for a second estimate of QD from the diffusion coefficient of oxygen in 6 iron at 1450" ~,~ we used the theoretical expression:3 (a = length of elementary cube edge, m = mass of interstitially diffusing atom, sM = migration entropy), applicable to diffusion via the octahedral interstices in bcc lattices. Taking sM = 3.8 k (migration entropy of carbon in a iron), one gets Q = 0.90 ev. Hence, in Ref. 3 Q = (0.98 *0.1) ev was proposed as a plausible value for the diffusion energy of oxygen in bcc iron. sM + 9 (9 = solution entropy for oxygen in bcc iron) can be determined from permeability measurements.4 Using the above-mentioned estimate for QS , the following expression for the solubility c (atomic concentration) of oxygen (in thermodynamic equilibrium with solid FeO) in bcc iron was derived: From [4] the solubility of oxygen at 881°C in a iron is calculated to lie between 0.6 and 12 at.-ppm. We see that the solubility determined by Swisher and

Jan 1, 1969

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron' and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970

By H. L. Marcus, P. W. Palmberg

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by Varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26" +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.' Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.' As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr, Ni, Sb, Mn, P, Sn, and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW' in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By AIME AIME

YOU can place an exclamation point after the "and How" if you want to, but the way it stands it sum¬marizes the Mining Geology sessions quite nicely; "Why" in the morning, "How" in the afternoon. It is altogether fitting that Prof. McLaughlin and Reno Sales, who have themselves achieved enviable reputations in company work, should have led the program by presenting informally a chapter from the volume dedicated to the beloved dean of all economic geologists, Waldemar Lindgren. In opening the morning session, over which Sydney Ball presided, Donald McLaughlin emphasized the continuous role mining geology should play in operating technique. He pointed out the importance of structural relations in a broad sense, and the preponderant role they play in developing the manner of ore occurrences. He illustrated this by an account of the work at Homestake, using slides to show the stratigraphic sequence, the folding, and the orebodies of that camp. An interesting piece of detail was the distinction they found could be made be¬tween the chlorite near the ore masses, and that in the country rocks. Whether the cummingtonite, characteristic of the rock in which the ore is found, is of regional or of contact metamorphic origin caused some discussion. Dr. Lindgren inclined to the belief that it was contact, but L. C. Graton replied that they had found the weight of evidence was for a hydrothermal origin. D. F. Hewett raised the question as to whether, in the advancing development of the mining industry, there was still a place for the U. S. Survey geologist, and the consensus seemed to be that there should be. His role is changing from that of mapping mining districts in detail, now the task of the companies, towards a more general serving of the industry through the wider perspective his work gives him in contradistinction to the greater detail of knowledge accumulated by the resident geologist.

Jan 1, 1933

By E. P. Abrahamson II

The effect of transition elements which form binary solid solution upon the recrystallization temperature of zirconium has been investigated. All additions raised the recrystallization temperature. A correlation is obtained between the logarithm of the rate of change of recrystallization temperature with atomic percent solute and the free atom ground state electron configuration of the solute element. ThE work of Abrahamson, et al., on dilute binary solid-solution alloys indicated a correlation between the free-atom ground state electron configuration of the solute and either the brittle-ductile transition or recrystallization temperature. These studies were carried out on bcc base materials. The implication is that the outer s and d electrons of the solute are the prime determinant of the absolute rate of change of recrystallization or transition temperature. Furthermore, the limit of linearity has been shown to be a function of solute electron configuration for recrystallization in iron and vanadium. To date no Complete systematic recrystallization study of dilute binary zirconium base alloys has been made. It is the purpose of this study to note whether the change in solvent structure from bcc to hcp will influence the correlation. It was also desired to learn more of the role of the electron configuration of the solvent on recrystallization temperature. PROCEDURE All alloys were made using 99.87 pct Zr with 0.01 Cr, 0.04 Fe, 0.006 Hf, 0.003 Mg, 0.003 Mn, 0.003 N, and 0.080 0 (132 BHN). The solute elements were 99.9 pct pure. According to the published binary phase diagrams6 and metallographic examinations at X750, all alloys used were solid solutions. The alloys were arc melted and remelted six times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot pressed at 950°C to 0.450 in., upset pressed to 0.350 in., and annealed at 800°C for 1 hr. The specimens were then Blanchard ground to 0.250 in., removing 0.050 in. from each side. The grain size of the material at this stage was found to be 8000 100 grains per sq mm. The specimens were then cold rolled to 0.130 in. and cold pressed to 0.125 in., yielding 50 1 pct cold work. All alloys were then chemically analyzed for the principal addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The rolled sheet was cut into 6.75 by 0.25-in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was 250o to 900°C over the 6-in. length, recorded continuously by six thermocouples resting on each specimen. Control was 3oC, accomplished at the hot end. The recrystallization temperature was determined metallographically using polarized light. The criterion chosen was the point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be 3°C. RESULTS Three different pure zirconium specimens were tested, and the recrystallization temperature was

Jan 1, 1962

By M. A. Grossman

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of unhardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of o.-2o per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as would appear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.2o per cent Mo provides a factor of 1.63, an increase of over 6o per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater harden ability will be obtained by using, for example, o.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

D. M. Riordan has been appointed a member of the Institute Com¬mittee of the Engineers' Reserve Corps movement. Our Committee, therefore, now consists of Henry S. Drinker, Chairman, Messrs. Arthur S. Dwight, Warren A. Wilbur and D. M. Riordan.

Jan 1, 1916

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By A. S. Odeh

During the last few years, several authors1-6 have advanced mathematical solutions, both exact and approximate, to the pressure behavior of a well producing from a region bounded by a circular discontinuity. The most recent solutions were reported by Carter, and by Bixel and van Poollen. Varter solved the appropriate equations analytically. Bixel and van Poollen reported a numerical solution and provided correlation charts for the interpretation of flow tests; their method uses an overlay technique and is valid for wide ranges of mobility and storage capacity ratios. The mobility ratio is defined as the ratio between k/p of the two zones, and the capacity ratio is defined as the ratio between $c of the two zones. We have developed independently an analytic solution, programmed for the CDC 1604, that agreed with Carter's.'1 The same differential equation, assumptions, boundary, and initial conditions were used. We ran 30 drawdowns and 30 buildups of a unit capacity ratio and of varied mobility ratios. We also varied the radial distances to the discontinuity, and the radii of drainage. We examined the results and obtained correlations that were simple to apply and useful in flow test interpretation. The results and the correlations reported here in graphical form allow the determination of the mobility of the two zones and the radial distance to the discontinuity. They eliminate the need to fit field data to a curve as is required in the overlay technique.6 Thus, the advantages of the present correlations are that they require less effort and they provide a unique answer. They also provide guidelines for selecting the parts of the flow test plot to be used in the interpretations. Moreover, the results obtained from the programmed analytic solution define the time intervals where the approximate solution reported by Hurstl and discussed by Larkin2 are applicable. Normal buildup and drawdown plots resulted in an early straight line, a long transition zone and a late (second) straight line. However, the second straight line will not occur if the drainage radius is not at least 10 times the radial distance to the discontinuity. The mobility of the imer and outer zones can be calculated from the slopes of the first and second straight lines, respectively, by the normal methods of the flow test analysis. We found that the radial distance to the discontinuity may be determined from the abscissa value for the point of intersection of the extensions of the two straight lines. Results similar to some of these were reported by Adams et aL7 The approximate solution compared favorably with the exact one during the first and second straight-line periods. However, during the transition zone, deviation occurred between the two solutions. Discussion of Figures Figs. 1 through 7 summarize the results of this investigation. On Figs. 3 through 7 there appears the equation of each respective plot. In this paper the mobility ratio M is defined as klp2/kzpl, where subscripts 1 and 2 refer respectively to the inner and outer zones, and dimensionless time = t, = 6.32 X In the investigation, M ranged from 0.25 to 50;

Jan 1, 1970

By J. B. Clark

In 1933, R. paris1 published a phase diagram for the entire Mg-Ca-Zn system. He reported the existence of a ternary intermetallic phase, Mg5Zn5Ca2, which formed a quasi-binary with the magnesium solid solution. Since then, no extensive work has been reported on the system. Recently however, indications of the existence of a second ternary in-termetallic phase in equilibrium with the magnesium solid solution led to a reinvestigation of the solid phase equilibria involving the magnesium solid solution. The 335°C (635°F) isothermal section was chosen for study. Metallography and powder X-ray diffraction were selected as the best mutually corroborating methods for determining the solid phase constitution. Seventy-six alloys were prepared from singly sublimed (99.95 pct) magnesium, electrolytic (99.95 pct) zinc and USP calcium. The analyses of some of the alloys are shown in Fig. 1. The alloys were melted in a graphite crucible under a chloride flu and chill cast in a split graphite mold. Dif-fusion couples (see Fig. 2) were prepared by casting molten Mg-20 wt pct Zn alloy around a cylinder of Mg-30 wt pct Ca alloy. The alloy samples and the diffusion couples were sealed under argon in Pyrex vials and annealed in a furnace capable of controlling within 1/2°C of 335°C. At the conclusion of the anneal, the alloy samples were quenched in ice water and the diffusion couples were air cooled. Procedures standard for magnesium alloys were used for metallographic examination. Powder X-ray diffraction patterns were taken on a G. E. camera with a 14.32 cm dim using nickel-filtered copper radiation. The redetermined 335°C (635°) section of the Mg-Ca-Zn phase diagram is shown in Fig. 1. TWO ternary intermetallic phases, designated w and

Jan 1, 1962

By C. A. Stiles, J. W. Nyhus

Erie Mining Co. is a 10.3-million-tpy pellet producer on the east end of the Mesabi Range 60 miles north of Duluth. Its complex includes facilities for mining, crushing, grinding and beneficiation in addition to a pellet plant and power plant. A 74-mile railroad links the mine and plant to Taconite Harbor on the shore of Lake Superior. The concentrate recovery ratio at Erie is about 1: 3, and this, along with stripping activity, makes it necessary for the company to mine nearly a million tons of material a week. At the outset, all crude ore mined at Erie was hauled entirely by rail, but with expansion into additional mining areas, the company made a gradual transition towards truck-to-rail haulage. Today, in Erie's 11th year of operation, over 50% of all crude taconite mined is transported by truck to loading pockets where it is transferred to rail cars. Future years will see more taconite moved in this manner. Thus, the company has an increasing interest in tire performance.

Jan 6, 1969

By A. H. Daane, B. J. Beaudry

The Sc-Y and Sc-Zr systems were studied by thermal and X-ray methods. Both systems are characterized by complete solid solubility in the low temperature hexagonal form and in the high temperature bcc form. In the Sc-Y system, there is a minimum in the solidus at 50 at. pct and 1365°C, while the solidus in the Sc-Zr system follows a nearly straight line relationship between the melting point of scandium and zirconium. There is a minimum in the temperature of transition from hexagonal to bcc in the Sc-Y system at 43 at. pct Y and 1175°C; while the temperature of transition is raised in the Sc-Zr system to a maximum of 1415 °C at 30 at. pct Zr. INTEREST in the metals of the first transition series has usually stemmed from their useful properties; however, there is now a great deal of interest in determining the fundamental nature of these metals. Since scandium is the first of these transition metals, a study of the preparation and Properties1 and the alloying behavior of scandium2 was initiated. In a continuing study of the alloying behavior of scandium, the systems of scandium with zirconium and yttrium have been established. Extensive solid solubility in both the Sc-Zr and Sc-Y systems was expected from application of the classical rules of Hume-Rothery. Also, the modified Darken and Gurry plot as suggested by Gschneid-ner3 showed ideal conditions for solubility in the Sc-Zr system with less favorable conditions in the Sc-Y system. The effect of scandium on the transformation temperature of zirconium and yttrium was of interest, since a recent empirical observation by Uly and Burr4 predicted that the solute scandium would raise the transformation temperature of zirconium and lower the yttrium transformation. In addition to noting the validity of the above predictions, the SC-Y and Sc-Zr systems were established. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar zirconium, distilled scandium prepared by the method described by Spedding, et al.1 and yttrium prepared by the method described by Carlson, et a1.5 The major impurities present in these metals are listed in Table I in ppm. Alloy Preparation. All the alloys examined were initially formed by comelting the two metals in a nonconsumable electrode arc-melting furnace under an atmosphere of purified helium or argon. The buttons were inverted at least five times and re-melted each time to ensure homogeneity. During preparation of Sc-Zr alloys, approximately 1 wt pct was lost which was attributed entirely to the loss of scandium by distillation. When preparing Sc-Y alloys, approximately 1.5 wt pct was lost, but it was assumed that the intended composition was maintained, since the relative weight lost when arc melting the component metals was nearly the same. Samples weighing 15 to 20 g were prepared for time-temperature thermal analysis, while only 1- to 2-g samples were prepared for the optical pyrometer and X-ray diffraction studies. Thermal Methods. The solidus and the melting points of the metals were determined by an optical pyrometer method described previously.2 The temperatures at which the transformation from hexagonal to bcc occurs were determined by differential thermal analysis. Several points on the solidus and liquidus in the Sc-Y system were also determined by this method and are in good agreement with those obtained by the optical pyrometer method. The procedure followed in the preparation of samples for thermal analysis and the furnace used have been described elsewhere.2'6 Since a limited quantity of scandium was available, most of the alloys were not melted during thermal analysis, thus avoiding contamination by the crucible. The alloy could then be reused and the composition changed by adding the desired quantity of solute to obtain the next alloy. Heat Treatment and X-Ray Methods. In order to ensure homogeneity, the "as arc-melted" alloys Were wrapped in tantalum foil, sealed in quartz capsules and heated at 1100°C for 15 hr and then cooled at a rate of 8 deg per min. Samples for X-ray diffraction were filed from these heat-treated alloys, sealed in 1/8 in. by 1/2 in. tantalum capsules under

Jan 1, 1963

By Elmer A. Jones

Like the caboose on the end of a long freight train L made up of mineral and metal processing and consuming industries, the mining industry progresses according to the movement of the train to which it is coupled. Sometimes the caboose rolls smoothly; occasionally it bumps along on the ties; almost always it is under criticism from someone for being too small, too large, too expensive, foolishly progressive, or hopelessly out of date. We who ride in the caboose are used to the rough by now, but it is nice now and then to have a bit of the smooth. Last year the train of industrial production rolled ahead swiftly and smoothly, and, except for a hot-box caused by strikes in copper mines, so did the caboose. As is brought out elsewhere in this issue, the outlook for 1956 is for more of the same.

Feb 1, 1956

By Robert B. Kistler, Ward C. Smith

The borate industry is one of the few sectors of the mining and mineral-processing industry which the United States still dominates. Since about 1927, the United States has supplied over half of the world's total boron and borate raw materials, and many of the chemical derivatives as well. Chiefly responsible for this record are companies producing sodium borates from two large deposits in southern California, at Boron (Kramer) and Searles Lake. The sodium borates, or products derived from borax and borax-containing brines, are the preferred borates for industry because they are soluble in water and combine readily with most other chemicals. Calcium borates (or sodium-free compounds) are required for certain end uses, but in general, nonsodium borates are used only where borax is not avail- able. During the past hundred years, the use of boron compounds throughout the world has risen from a few tons per year to the equivalent of about a million tons of B2O3. Leadership in supplying borates has shifted from country to country and from region to region during this period, generally as the result of the development of newly discovered deposits that were better in quality, more accessible, or more economically exploitable than previous sources (Table 1). Primary Products and End Uses The principal borate products offered by primary producers in the United States are listed in Table 2. In general, these products are utilized worldwide by almost all consumers, regardless of the original source of the primary borates. In the United States, the primary borates all originate in southern California. Colemanite is produced as crude or processed crude ore from the Death Valley area and is utilized by the fiber glass and ceramic industries without further treatment. Production from Searles Lake, Calif., is from brines that are processed in chemical plants where borax and other compounds are recovered and the principal borate products are produced. At Boron, Calif., the world's leading producer is mining a deposit of mineral borax and operating a chemical refinery. The mineral borax is mined together with included clay, and refined borax or "lo-mol" is one of the refinery products. The mineral and the chemical compound are identical, Na2B4O7- lOH2O. In addition to ship- ping all major refined borate products from Boron, the company ships semiprocessed ore concentrates to treatment plants elsewhere.

Jan 1, 1975