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By A. H. Duane, A. E. Miller

The high-temperature allotropy of some heavy rare-earth metals and their alloying behavior with magnesium in the 0 to 50 at. pct Mg region was studied by thermal, microscopic, and X-ray methods. Examination of a hcc phase retained upon quenching alloys of different magnesium content confirmed the existence of a bcc high-temperature allotrope in pure gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. The lattice constants of the pure metals were determined from a Vegard's Law extrapolation and .found to be 4.05, 4.02, 3.98, 3.96, 3.94, 3.92, and 3.90 + 0.02 A, respectively. In all of the systems studied, the high-temperature bcc phase decomposed eutec-toidally, when slowly cooled, into a hexagonal rare earth-Mg solid solution and a simple-cubic peritec-tic AB-type compound. In 1956, Spedding et al.' observed high-temperature resistivity anomalies in the light rare-earth metals and made several unsuccessful attempts to retain the high-temperature form of these materials at room temperature by quenching the pure metals from temperatures near their melting points. High-temperature X-ray techniques were used by Spedding et a1.' in 1959, to investigate the high-temperature allotropy of the rare-earth metals. This study showed that lanthanum, cerium, praseodymium, neodymium, ytterbium, and possibly gadolinium are bcc at temperatures near their melting points. Discontinuous changes in resistivity at elevated temperatures were also observed for pure gadolinium, terbium, dysprosium, holmium, and lutetium, thus indicating the possible existence of a high-temperature crystalline transformation in these metals. However, due to experimental difficulties encountered in the high-temperature X-ray analysis of these metals, their allotropic form was not identified. Spedding et a~.~ in 1960 observed that yttrium displayed a continuous solid solubility with lanthanum at elevated temperatures, thus showing the high-temperature structure of yttrium to be the same as that of lanthanum, i.e., bcc. Similarly, the high-temperature alloying behavior of gadolinium with yttrium showed gadolinium to be bcc at elevated temperatures. The bcc nature of the high-temperature form of yttrium was again recognized in 1960 by Eash and carlson4 in their study of the alloying behavior of yttrium with thorium. Gibson and Carlson, in a similar study of the alloying behavior of yttrium with magnesium, found that by quenching Y-Mg alloys from within the 0-solid solution region, Fig. l, they were able to retain the allotropic form of yttrium. It was the present authors' intention to use this method to show the existence of a bcc high-temperature form of the heavy rare-earth metals gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. Simultaneous with the present work, Beaudry and Daane' have shown the bcc nature of the high-temperature form of scandium. EXPERIMENTAL PROCEDURES Materials. The rare-earth metals used in this study were prepared by the calcium reduction of the fluoride and were further purified by vacuum distillation. The magnesium was obtained from the New England Lime Co. and was also purified by distillation prior to its use in the preparation of the rare earth-Mg alloys. The results of chemical and spec-

Jan 1, 1964

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain' extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami's reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969

By U. N. Bhrany, N. Arbiter

F. C. Bond (Consulting Engineer, Processing Machin-Dept., AllisChalmers Manufacturing Co., Milwaukee) This is a very comprehensive paper. It deals with 1) size distribution functions, 2) energy-particle size relationships, and 3) criteria for grinding efficiency. The method of analysis used consists of tracing the increase and decrease of successive Tyler scale screen fractions as grinding progresses. The treatment is based upon the assumption that the work done in grinding is concentrated entirely upon the coarse size fractions in the mill. It is postulated that when a feed consisting entirely of particles of one size fraction is batch ground that finer fractions increase at a constant rate as grinding progresses, until finally each in turn begins to be ground and to decrease in amount. It is shown that under these conditions the empirical Gates-Gaudin-Schuhmann log-log size distribution plot can be logically explained. It is difficult to imagine any condition of ball mill operation, or any probability analysis, which would result in no grinding contacts on the finer particles present. However, the authors' postulate must be accepted if their conclusions are to be sustained. They conclude that the equation expressing the for mation rate of each size fraction can be resolved into the G.-G.-S. size distribution equation, and that the curvilinear portion of the log-logsize distribution line represents the only particle sizes which are being ground as well as produced. The author's statement that the G.-G.-S. Eq. 4 applies only to the finer portion of the size distribution while the Rosin-Rammler Eq. 6 applies over the whole size distribution range certainly supports the view that an exponential equation of the Rosin-Rammler type corresponds more closely to actual size distribution than does the power law G.-G.-S. equation. However, the G.-G.-S. equation is used to derive Eq. 8 and Eq. 9, which state that the energy required to grind a ton through a particular mesh varies inversely as the particle size to the exponent -a , whic h is the slope of the extended G.-G.-S straight line. This is stated to apply to both batch and continuous grinding. The G.-G.-S. slope exponent thus becomes very important in all crushing and grinding analyses by this method. The authors include some data which can be used to test their conclusions, as described below: We will consider grinding a feed composed of 14 mesh (1190u) to -200 mesh (74u). The average of 17 Allis-Chalmers grindability tests on quartz gives a work index (Wi) of 12.77. The -200 mesh product should have 80 pct passing 41.6u or P = 41.6. The equivalent 80 pct passing size of the 14 mesh feed particles is considered to be the particle diameter, as is true for spherical particles. Thus F is 1190u. In the work index equation 10 wi 10 wi 127.7 127.7 P f 41.6 1190 = 16.1 kw-hrperton. In Table I the ball mill exponent for quartz is 1.0 and from Eqs. 9 and 10: w=kw-hr/ton =Constan/(do/di) = 16.1 ton so that (1190) Constant/ Constant and the Constant equals 259. The tons per horsepower-hour value is 0.0464, in agreement with Table IV. The exponents for other minerals are listed in Tabl e 11. In Table IIA, the kilowatt hours per ton required to grind these minerals between the same sizes as the quartz, both by the authors' method and the work index equation, are listed. According to the authors kw-hrperton = 259/(16.1)".

Jan 1, 1961

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By AIME AIME

IV. THE BOUNDARY BETWEEN STEEL AND IRON. It would be well to decide on a definite carbon-content to serve as a boundary line between ingot-iron and ingot-steel, between puddled-iron and puddled-steel, and between any other varieties of wrought-iron and weld-steel. Two plans have been considered. One is to draw this line at 0.32 per cent. of carbon or its equivalent in other elements, for the reason that this carbon-content appears to correspond to the critical point, 0, in the diagrams of Roberts-Austen and Rooze-boom.8 This has the merit of corresponding to a definite physical boundary. The other plan is to draw the boundary at 0.20 per cent. of carbon, because this is a convenient place to separate the important classes " soft steel " and " half-hard steel," so that if this point was adopted "ingot-iron " would be synonymous with "soft steel," and " ingot-steel " would be the equivalent of the two classes, " half-hard steel " and " hard steel."

Mar 1, 1908

C. W. Kempton, Oro Blanco, Ariz.: In his interesting paper, Mr. Ingalls refers to reports of tin-deposits near Sain Alto, Zacatecas, Mexico. During 1891 I made some personal examinations of these deposits. They are, for the most part, located from 10 to 30 miles west of the town, in the Sierra del Fraile.

Jan 1, 1896

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By G. K. Manning, W. E. Few

T has been known for some time that both&apos;inter-granular carbide and intergranular oxide phases cause brittleness in molybdenum. Parke and Ham&apos; indicated that 0.0025 pct 0 present in molybdenum after solidification from the melt was sufficient to induce intergranular brittleness during forging. However, material containing 0.06 pct C could still be forged. However, adding this amount of carbon to insure deoxidation causes the formation of carbides on freezing. These carbides are precipitated at grain boundaries, and Rengstorff and Fischer&apos; have shown they have an unfavorable effect on the room-temperature ductility of molybdenum. Take? in 1928 proposed that the solubility of carbon was a constant value of 0.30 pct from room temperature up to 1800°C. In 1935, Sykes, Van Horn, and Tucker&apos; obtained X-ray data suggesting that the solid solubility of carbon in molybdenum was between 0.07 and 0.09 pct at temperatures from 1500" to 2100°C. The a-solubility line for carbon was included in the Mo-C diagram given in the Metals Handbook as a tentative line based on the data of Sykes, Van Horn, and Tucker. In order to determine the partial phase diagrams for these systems, it was necessary to construct a high-temperature furnace suitable for heat treating molybdenum at temperatures up to 4000°F. A molybdenum resistance furnace was built for this purpose in which samples could be heat treated in a purified atmosphere and quenched from any desired temperature.&apos; Experimental Work Solubility of Carbon: Arc-cast molybdenum supplied by the Climax Molybdenum Co. and 18-gage molybdenum wire samples produced by powder metallurgy at the Fansteel Metallurgical Co. were used in determining the a-solubility line for the MO-C system. The cast molybdenum contained 0.032 pct C initially. Two lots of 18-gage wire were used, one containing 0.011 pct C and the other 0.005 pct C initially. All material contained a carbide phase as received. Fig. 1 illustrates the carbides found in the untreated material. Heat treatment in a purified hydrogen atmosphere was found to reduce the carbon content in the as-cast molybdenum. Purified argonT also decarburized molybdenum samples at temperatures above 3500°F; however, the carbon content remained constant during heat treatment in purified argon at lower tem- peratures. The argon was purified by passing it over titanium at 750 °C and then through a magnesium perchlorate drying tower. The hydrogen was purified by passing it through a commercial hydrogen deoxidizer, followed by a drying tower. Specimens having different initial carbon contents were heat treated in argon at 3500°F for periods ranging from 5 min to 5 hr and were analyzed for carbon. Samples of the same final carbon content had the same microstructures regardless of time at temperature. Furthermore, a gradient between center and surface in the amount of undissolved carbide particles present was never observed. It was concluded that at these low carbon levels, and at the high temperatures involved, diffusion proceeds so rapidly that the specimen is always substantially homogeneous in carbon content, in spite of the gradual loss in carbon. Based on the above findings, the following procedure was used to determine the carbon-solubility limit at 3000°, 3500°, and 4000°F. At each of these temperatures, a number of samples were heat treated, as shown in Table I, and rapidly cooled to room temperature. Since the samples lost carbon in proportion to the length of time heated, a series of samples were obtained of varying carbon contents. By use of a rapid cooling rate, the phases present at the high temperature were retained at room temperature. All samples were examined microscopically. Those found to contain either no excess carbide phase or only a very small amount were then analyzed for carbon. The samples actually analyzed for carbon

Jan 1, 1953

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.&apos; Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry&apos; for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

By C. E. SWANN

NOT long ago an engineering study was made to determine if the time had arrived to lower the head of standing water in abandoned Rock Springs mines Nos. I and 3 of The Union Pacific Coal Co. so that this water would not become a menace to the future operations of adjacent mines or mines developed on seams lower in the coal measures. This survey resulted - in a decision to unwater the No. 1 mine workings and, incidentally, the old No. 3 mine workings by drilling a large-diameter hole from the surface to an opening in No. 1 mine at the sump below 21 entry, provided it was found practical to operate a large-capacity, vertical, deep-well pump under the existing conditions. This would relieve the static bead of 200 ft. of water at the fault that separates Rock Springs mines Nos. 1 and 4, which is the

Jan 1, 1935

By AIME AIME

ALTHOUGH the retiring Chairman of the Industrial Minerals Division, Charles Henry Behre, Jr., does not say "you all" he is a product of the deep South, since he was born at Atlanta, on March 16, 1896. At the Boy Scout age he moved to New Orleans, where his father owned an ice plant, which seems an intelligent business for that climate. Intelligence evidently runs in the family, for Charlie, as his friends call him, has one sister who is a professor of zoology and another who is a concert pianist. Charlie has no explanation of why, when he reached college age, he decided to go to the University of Wisconsin, other than something more than an ordinary boyish interest in science, and the reputation which Wisconsin then enjoyed. At Madison he fell under the influence of Eliot Blackwelder, chose paleontology as his objective, and transferred, at the end of his sophomore year, to the University of Chicago, where the paleontological panorama seemed more extensive. He took his B.S. there in 1918, and graduated into the U. S. Army, where he eventually became a Sergeant in the Medical Corps.

Jan 1, 1945

Jan 1, 1895

By J. G. Balkestein, J. W. R. Baerts

During an attempt to develop a method for accurate, rapid, continuous analysis of ash content of wal, the Dutch State Mines Laboratory found that the absorption coefficient for X-rays was related to ash content. This relationship was utilized in the development of an apparatus called CendreX, used to measure the absorption and in turn the ash content. The principle, procedure, accuracy, and applications of the CendreX automatic determination of ash in coal are discussed in detail. Until recent years coal preparation research was concentrated on the possibilities and efficiency of preparation equipment. Ever increasing demands for quality in coal, however, have caused researchers to become concerned with quality control. One of the characteristics strongly influencing quality (calorific value) and, consequently, the price of coal is ash content. Both customer and producer require that the ash content be controlled. To make this possible it is necessary for the producer to collect samples from the coal stream in the washery and to determine their ash content. On the strength of the results obtained the production process can then be adjusted, if required. Until recently incineration was the only method for determining ash content. When coal is incinerated with oxygen, it takes at least 15 min to determine the ash content. Even then some time may be lost in passing on the data. Therefore, this discontinuous and time-consuming method does not make a suitable starting point for checking, re-adjusting, or modifying the production process. Since it was not possible to accelerate incineration by mechanization and automation, another type of rapid continuous analysis had to be found. This would have to depend on some coal characteristic closely linked with ash content. At the Central Laboratory of Dutch State Mines, Dijkstra and Sieswerda found that the absorption coefficient for X-rays was suitable for this purpose. An apparatus based on the measurement of this characteristic was developed. Named CendreX,* this patented equip- *A Stamicarbon N. V. registered trademark. ment, used in combination with a sampler and conditioning apparatus, permits continuous determination of ash content with satisfactory exactness to within 3 min.t At the American Mining Congress meeting of May 1961, Log A. Updegraff, surveying aspects of continuous analyaia, reported on the CendreX appartus (Mining Congress Journal, August 1961). Since the first Condition for correct ash determination, whatever the method used, is always a sample taken in the right way, some practical aspects of sampling will be discussed first. SAMPLING In coal handling operations, each grain has its characteristic properties. In both the cross-sectional and longitudinal direction of the product stream the mixture of these grains is imperfectly blended. The elimination of the factor of segregation between the cross-sections from the direction of the stream is the principal aim of continuous analysis. Therefore, the samples to be analyzed are withdrawn in various places from the segregated product stream in such a way that they form a semi-continuous flow. In order to be truly representative of the product stream, the sample flow must fulfil two conditions: 1) The sample flow must be sufficiently large to insure that adventitious differences between the composition of the product stream and sample flow will be as small as possible. 2) All grains through the entire cross section of the product stream must have an equal chance to get into the sample flow. Since there is always a segregation through the cross section the sample flow will have a bias if the sampler collects only part of this section. In order to prevent the volume of the sample flow from becoming too large, the cross sections are taken discontinuously. However, this discontinuity gives rise to the adventitious differences that arise between the composition of product stream and the sample flow, and these differences become greater and are more deranging as the fluctuations follow each other more quickly. Moreover, the intervals between the morrnents of sampling mean a delay in the analysis. The aim will, therefore, be to collect small samples, or in other words thin cross-sectional increments, taken at sufficiently high frequencies. The following points should also be taken into account: 1) The smallest dimension of the openings in the sample collector must be equivalent to at least 3 d in

Jan 1, 1962

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

The microstructural stability of 59 carbon and low alloy steels after 34,000 hr exposure at 900&apos; and 1050°F, including the weld heat-affected zone, is discussed. The tensile and creep rupture properties of the parent metal of many of the steels before and after 10,000 hr exposure are presented. SEAMLESS pipe has been used for many years at elevated temperatures. When seamless first began to be used, operating temperatures and pressures were relatively low and the steel produced adequately met the existing requirements. The need for knowledge of creep properties and graphitiza-tion was nonexistent. Today the requirements for tubular products have changed considerably. Operating temperatures and pressures are increasing continually and corrosion, particularly at high temperatures, presents a problem. Carbon steels have, under these conditions, certain economic advantages particularly in oil refinery use. However, the use of low alloy steels in the generation of steam power has increased appreciably due to the influence of molybdenum on creep strength and the control of graphitization with chromium. The behavior of carbon and certain low alloy steels after long periods of exposure at 900° and 1050°F (480° and 565°C) has been investigated. The steels were examined before and after 10,000 to 34,000 hr exposure. Results obtained with material exposed at 1200°F (650°C) are not presented due to the severe oxidation and resulting decarburiza-tion after long periods of exposure. The graphitization characteristics of carbon and low alloy steels are of fundamental concern to the users of these materials. This is particularly true where welded joints are employed. In order to evaluate properly the behavior of steels at elevated temperatures, it is desirable to employ not only long periods of exposure under controlled conditions, but to use material with known properties and steelmaking practices. The purpose of this investigation has been to study the microstructure of the weld and the tensile and creep rupture properties of the parent metal after long periods of exposure at elevated temperatures. In the report&apos;.&apos; of a previous investigation data were presented on the microstructure, impact strength, hardness, and oxidation characteristics after 10,000 hr exposure at elevated temperatures. When this investigation was planned, methods for controlling the graphitization characteristics of steel were not established and, therefore, a number of special alloy steels were included in the study. During the exposure of these steels, the influence of aluminum in accelerating the rate of graphitization and the inhibiting power of chromium were established by various investigators. Also, the vanadium-bearing steels, because of their outstanding creep properties, received attention. As a result of these developments, considerable progress has been made in the field of high temperature tubular products, and the necessity for special alloys to prevent graph-itization has been restricted largely to the use of chromium. Material Chemical analysis, deoxidation treatment, and austenitic grain size of the 59 steels discussed in this paper are shown in Table I. The steels were forged to 1x1 in. bars with the exception of steels 12B, 12DX, 12DY, 12DZ, 70, 70A, 72 to 78, 82, and 83 which were machined from heavy wall pipe. All bars were surface ground before exposure. Heat treatment before exposure is shown in Table 11. The majority of the steels included were melted in either a basic open hearth or basic electric furnace; how-

Jan 1, 1955

By D. G. Westlake

Alloys of poly crystalline Nb-H have been tensile tested at 77" and 120°K after slow-cooling and after quenching from room temperature. A rationale has been developed to explain the effect of cooling rate on ductility in terms of microstructure. The inferior ductility of the slow-cooled alloys in this temperature range can be attributed to the precipitation of coarse hydride particles that fracture in the early stages of plastic deformation. Quenching Produced much smaller hydride particles and a decreased tendency for initia-tion and popagation of cracks. Prismatic dislocation loops, punched into the matrix of quenched alloys, eliminate the yield point and may Play some role in the low temperature ductility of the quenched alloys. The difference in ductility between quenched and slow-cooled V-H alloys was even greater than that observed in the N b-H alloys. It is well known that the ductility of Nb-H and V-H alloys decreases with increasing hydrogen concentra-tion and with decreasing temperature.1-l1 The follow-ing are some of the numerous mechanisms that have been adopted in attempts to explain these observations: 1) hydrogen-dislocation interarction,4&apos;6 2) lowering of the crack surface energy by adsorbed hydrogen,9&apos;10 3) localized lowering of the niobium bond strength,9 and 4) exertion of pressure inside voids by molecular hydrogen.6 A recent study1&apos; indicates that, in some way, the embrittlement is related to the precipitation of a hydrogen-rich phase, because embrittlement and hydrogen solubility have the same temperature dependence. Most of the investigators observed that at very low temperatures there was a return of the ductility. Thus, hydrogenated niobium and vanadium may be said to exhibit a low temperature ductility minimum."1&apos;8&apos;9 It has been reasoned by most observers that diffusion is required for the embrittlement mechanism to be operative, and that as hydrogen becomes immobile at very low temperatures, the ductility increases. This investigation of the mechanical behavior of Nb-H al-loys under various conditions is an attempt to gain a better understanding of the low temperature ductility minimum. EXPERIMENTAL Tensile specimens, with gage length dimensions 20 by 3 mm, were machined from sheet stock" and both faces were ground on wet 600 grit Sic paper to obtain a final thickness of 0.5 mm. Annealing as described earlier12 resulted in average grain diameters of 0.3 mm. The recrystallized niobium tensile specimens were electropolished in 90 parts H2S04, 10 parts HF (48.9 pct) by volume, at 287°K and 30 v. Hydrogen, which may have been present in the starting material and/or added during specimen preparation, was removed by annealing at 1073°K in a dynamic vacuum of 2 X 10-6 torr. Hydrogenated specimens (1.15 at. pct H) were prepared by reaction with a known quantity of pure hydrogen (obtained by thermal decomposition of UH3) at 1073oK, followed by cooling at the rate of 100" per hr. These were vacuum encapsulated, homogenized at 573°K for 3 to 5 hr, and furnace-cooled. Tensile tests were conducted on an Instron machine at a strain rate of 4 x l0-5 per sec. The gripping device was such that the specimen was positioned below the crosshead. Thus, subambient test temperatures could be obtained by immersion of the device in a cooling bath of either liquid nitrogen or Freon-12. The temperature of the Freon-12 was controlled within ± 0.1°K of the desired temperature by automatically monitoring the flow of liquid nitrogen through a copper coil in the bath. Slow-cooling to 77°K was accomplished as follows. The testing device was surrounded by a rubber jacket, open at the top and with small holes in the bottom. Liquid nitrogen, brought up to the bottom of the jacket, entered the holes and vaporized quickly. The temperature was monitored at the specimen with a copper-constantan thermocouple, and a constant cooling rate of 2 deg per min was easily achieved by controlling the level of the liquid nitrogen outside the jacket. RESULTS AND DISCUSSION Low Temperature Ductility Minimum. Resistometric studies of both Nb-H12 and V-H13 indicated that at tem-peratures less than 150°K, virtually all of the hydrogen

Jan 1, 1970

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By W. T. Stuart

THE increased demand for iron ore has necessitated a re-examination of ore-bearing lands on which the presence of water previously has indicated hazardous and expensive operating conditions. In view of the importance of iron ore production to the national economy and defense, the Ground Water Branch of the U. S. Geological Survey, in cooperation with the state of Michigan, began a study of mine drainage in the Iron River district in 1945, and later extended the work to the Marquette district. The purpose of these studies was to define the principles involved in the movement of surface and ground water toward the mined areas, with the hope that the information obtained in the research would lead to the development of methods of water control and to a reduction in the total mining costs. Not only are the direct costs of drainage increasing, but also the indirect operational costs of working a wet mine are becoming a larger proportion of the total mining costs. For some wet mines the direct costs of pumping and drainage may range from 35 to 40Ø per ton of ore produced, but the indirect costs due to handling wet ore and controlling the water may be five to ten times this amount. The methods of study were formulated as the work progressed, and inasmuch as they were the first large-scale studies of their kind, they should serve as a guide for the solution of similar problems in other mining areas. The Iron River district was chosen for a pilot study because in this district the longest records of mine pumpage and water-level observations were available, including, as they do, the records for the Homer mine of the M. A. Hanna Co., where pumping from surface wells began in 1930. The results of the first investigation by the Michigan Department of Conservation have already appeared." The first section of the report on a similar study of the Marquette district, which was started in 1948, will be published this year. Methods of Study In an effort to reduce the flow of water into the mine workings in the Iron River district, about 4500 gpm was pumped from the bedrock being mined and about 9000 gpm from the glacial overburden. In the Marquette district in the vicinity of Ishpeming and Negaunee, about 5000 gprn was pumped from the bedrock and about 4000 gpm was pumped from the glacial overburden. Where the water was pumped only from the bedrock, the rate of pumping ranged from a few hundred gallons per minute in the dry mines to many hundred gallons per minute in the wet mines. In each district, pumping from the overburden was localized on a few properties where costly pumping installations had been made and the expenditures for power had been large. In each district a comprehensive ground-water investigation was made of the whole area, involving the collection and interpretation of all the available data bearing on the source and quantity of water to be controlled. Although it is not the purpose of this paper to discuss the methods of making a ground-water investigation, it should be pointed out that a drainage study follows a pattern of engineering analysis that determines the occurrence, source, movement, disposal, and quantities of water involved. The investigation in the iron-mining districts of Michigan began with the construction of a map of the buried bedrock topography. Because the ground-water reservoirs occupy the low points in the bedrock basins, this map gives information concerning their areal extent, depth, shape, and degree of interconnection. The depth to water in the drillholes and wells indicates the altitude to which the ground-water reservoirs are filled, and the logs of the material penetrated in the drillholes and wells indicate the general character of the materials filling the reservoir. The slope of the ground-water surface indicates the direction of flow through the reservoir, the water movement being from the points of higher altitude to points of lower altitude. By analysis of the rise and fall of the ground-water levels in response to additions of water through recharge and to changes in the rate of discharge through pumped wells, estimates of the total quantity of water in storage and of the rate of flow through the reservoir

Jan 1, 1952

By W. A. Hoyer

A pulsed high-energy neturon-induced spectral logging tool has been built and field-tested. The reaction of deuterium on tritium is used to generate pulses of 14-Mev neutrons. By detecting only the prompt gamma rays produced by neutron inelastic reactions in the formation, the presence and relative abundance of carbon, oxygen, calcium, silicon and other important elements may be ascertained from a gamma-ray spectrum. Gamma-ray spectra obtained in a shallow test well and in experimental field use show that it is possible to identify formations and their contained fluids. INTRODUCTION The penetrating gamma rays from naturally occurring radioactive elements in subsurface formations have been used for a number of years in well logging as a means of characterizing and distinguishing strata. Still another nuclear logging method which has been employed for some years consists of the bombardment of strata with neutrons and the measurement of the number of gamma rays produced by neutron capture reactions involving elements in subsurface strata.&apos; Since one of the principal elements entering into capture reactions is hydrogen, the latter procedure essentially results in a hydrogen log, whether the hydrogen be in combined form in either oil or water; thus, the log gives an indirect measure of porosity. These methods, with various refinements, have been developed to such an extent that they have become routine procedures in formation evaluation. Neither gamma-ray logging nor conventional neutron logging, however, yields sufficient information to permit unequivocal identification of the mineralogic composition of formations, and neither method gives information which may be used for the positive identification of hydrocarbons in strata. Accordingly, a number of efforts have been made in recent years to gain additional information from nuclear logs. Brannon and Osoba have shown that it is possible to identify naturally occurring radioactive elements in subsurface formations by spectral analysis of gamma rays emanating from these elements. Such an identification is of value in the characterization of strata. A simplified form of spectral analysis of gamma radiation resulting from neutron capture reactions between elements in earth materials and bombarding neutrons has been used with some suc- cess under favorable conditions to differentiate between petroleum and water. This method relies upon the relatively high energy of gamma radiation from neutron capture by chlorine and, in effect, furnishes a chlorine log. In areas in which interstitial water is of sufficiently high salinity, this log can give valuable information on water saturation and, thus, indirectly on hydrocarbon saturation. Still another approach to obtaining more information by nuclear techniques is "activation logging", in which certain elements yield short-lived radioactive isotopes on neutron activation and, thus, can be detected by gamma-ray spectral analysis. From the standpoint of determining by nuclear logging methods the mineralogic composition of strata and the presence or absence of hydrocarbons, it is essential that information be obtained on the presence and relative amounts of several elements such as carbon, oxygen, hydrogen, calcium, silica and others. Some elements, such as hydrogen, chlorine and sulfur, can be determined by spectral analysis of gamma radiation resulting from neutron capture reactions."" Others — carbon and oxygen, for example — do not enter readily into capture reactions but do yield gamma rays of characteristic energies from inelastic scattering reactions with high-energy neutrons. Accordingly, the latter reactions are of particular interest as a means of identifying hydrocarbons in subsurface strata. Several years ago it was recognized that information requisite to the identification of subsurface strata and of contained fluids could be obtained by pulsed operation of a subsurface neutron generator and associated gamma-ray detector. It was contemplated that pulsed operation would be effective in discriminating in time that gamma radiation which results predominantly from inelastic scattering reactions from that gamma radiation arising from neutron capture reactions. Accordingly, research was continued and construction of such a device was initiated. Although many problems were encountered, they were solved successfully. The following sections describe the tool which has evolved, its performance and the results which have been obtained with it to date. THEORY OF OPERATION OF NEUTRON-INDUCED GAMMA-RAY SPECTRAL LOGGING TOOL THEORY OF INDUCED NUCLEAR REACTIONS Of fundamental importance is the fact that an element, when bombarded with neutrons, emits gamma radiation of energy characteristic of that element. In theory, therefore, an element may be identified by