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By Shiou-Chuan Sun, R. F. Wesner, J. D. Morgan

0. C. Ralston and F. Fraas—Dr. Sun and associates have presented an interesting paper not all of which is comprehended by us. The data assembled measure the deflections of particles in an electrostatic field as a function of a number of independent variables and some dependent variables that are not sharply differentiated. These data are all based on a Johnson type machine of definite, well-described geometry, something not often done in electrostatic separation literature. One new fact brought out by this technique is the effect of coal dust on admixed pyrite and quartz. The effects are opposite in character, as should be expected and we do not agree with the authors that these effects are negligible. Fraas' also used a multiple cell "distribution analyzer" and gives in fig. 5 of his paper a straight line plot with no humps or curves. This is not necessarily at variance with Sun's results because Fraas used a larger gap between electrodes and had no evidence of particles adhering to or dropping off the charged electrode. The section of Sun's paper on effect of surface conductivity contains a speculation that the dielectric constant "represents more or less the electrical conductance of the bulk body instead of the surface of the mineral particles." A simple picture of the meaning of the dielectric constant is that it is the specific inductive capacity of a dielectric when used as the dielectric between the plates of a condenser. It is at once evident that the above speculation confuses capacity with conductance—two definitely independent variables. We ask the authors to state in what group or subdivision their garnet belongs; what method and units were used in calculating the data of col. A, table I and their meaning; what was the temperature of the carrier roll and, finally, has any effort been made to investigate the effects of particle shape on distribution in the electrostatic field? S. B. Hudson—I have read this article with great interest. We have been engaged in research work on the principles of electrostatic separation in this laboratory for some time now, and our findings agree with those of the authors in many respects. The article shows evidence of careful and valuable research in the field of electrostatic separation. A "distribution analyser," very similar to that described in an earlier article by one of the authors," was incorporated in an inclined plate-type electrostatic separator designed and built in the Melbourne University laboratory in 1948 for investigation purposes.22 The actual splitting edges were machined from y! in. per-spex, and the paper hoppers were supported on linen thread immediately below the perspex dividers. These dividers fitted into machined slots in a framework to give accurate Yz-in. spacings. The hoppers (staggered) fed directly into a rack of test tubes, which is supported on a vertical pantograph arrangement. The rack was positioned with guides on the horizontal pantograph stand, and this ensured positive alignment when replacing the rack after making weighings. In later work, when much heavier feed rates were used, of the order of 30 to 40 Ib per in. per hr a rack fitted with rectangular metal containers and similarly aligned was used. Some work was done here on comparing the distributions of minerals when passed separately and when passed as a mixture, and it was found that there was quite an appreciable difference in the two results.= However, in our separator the particles do not pass down the plate in a single layer, and this difference is probably caused by collisions of one mineral particles with the other mineral particles. In most of the investigational work here, the change of the center point of the distribution is measured to establish the effect of a variable, such as voltage. Two minerals (zircon and rutile) have been studied rather exhaustively, and it was found that their distributions are very nearly normal. Owing to the sharpness of the distribution curves, the usual method of obtaining the mean or median was inaccurate, and was not used; instead the mean (also the median), calculated on the assumption of a normal distribution, was used to locate the center point of each distribution and proved satisfactory. The effect of polarity becomes very apparent in the plate-type separator where frictional charges play a very important part when using highly resistive minerals such as zircon. With rutile, a comparatively conductive mineral, polarity of the electrode has little effect. On the other hand, the magnitude of the voltage has a far greater effect on conductive than on resistive minerals. Shiou-Chuan Sun (authors' reply)—Thanks are extended to Drs. Ralston and Fraas for their keen interest in this paper. Their questions concerning coal dust,

Jan 1, 1951

By Shiou-Chuan Sun, R. F. Wesner, J. D. Morgan

0. C. Ralston and F. Fraas—Dr. Sun and associates have presented an interesting paper not all of which is comprehended by us. The data assembled measure the deflections of particles in an electrostatic field as a function of a number of independent variables and some dependent variables that are not sharply differentiated. These data are all based on a Johnson type machine of definite, well-described geometry, something not often done in electrostatic separation literature. One new fact brought out by this technique is the effect of coal dust on admixed pyrite and quartz. The effects are opposite in character, as should be expected and we do not agree with the authors that these effects are negligible. Fraas' also used a multiple cell "distribution analyzer" and gives in fig. 5 of his paper a straight line plot with no humps or curves. This is not necessarily at variance with Sun's results because Fraas used a larger gap between electrodes and had no evidence of particles adhering to or dropping off the charged electrode. The section of Sun's paper on effect of surface conductivity contains a speculation that the dielectric constant "represents more or less the electrical conductance of the bulk body instead of the surface of the mineral particles." A simple picture of the meaning of the dielectric constant is that it is the specific inductive capacity of a dielectric when used as the dielectric between the plates of a condenser. It is at once evident that the above speculation confuses capacity with conductance—two definitely independent variables. We ask the authors to state in what group or subdivision their garnet belongs; what method and units were used in calculating the data of col. A, table I and their meaning; what was the temperature of the carrier roll and, finally, has any effort been made to investigate the effects of particle shape on distribution in the electrostatic field? S. B. Hudson—I have read this article with great interest. We have been engaged in research work on the principles of electrostatic separation in this laboratory for some time now, and our findings agree with those of the authors in many respects. The article shows evidence of careful and valuable research in the field of electrostatic separation. A "distribution analyser," very similar to that described in an earlier article by one of the authors," was incorporated in an inclined plate-type electrostatic separator designed and built in the Melbourne University laboratory in 1948 for investigation purposes.22 The actual splitting edges were machined from y! in. per-spex, and the paper hoppers were supported on linen thread immediately below the perspex dividers. These dividers fitted into machined slots in a framework to give accurate Yz-in. spacings. The hoppers (staggered) fed directly into a rack of test tubes, which is supported on a vertical pantograph arrangement. The rack was positioned with guides on the horizontal pantograph stand, and this ensured positive alignment when replacing the rack after making weighings. In later work, when much heavier feed rates were used, of the order of 30 to 40 Ib per in. per hr a rack fitted with rectangular metal containers and similarly aligned was used. Some work was done here on comparing the distributions of minerals when passed separately and when passed as a mixture, and it was found that there was quite an appreciable difference in the two results.= However, in our separator the particles do not pass down the plate in a single layer, and this difference is probably caused by collisions of one mineral particles with the other mineral particles. In most of the investigational work here, the change of the center point of the distribution is measured to establish the effect of a variable, such as voltage. Two minerals (zircon and rutile) have been studied rather exhaustively, and it was found that their distributions are very nearly normal. Owing to the sharpness of the distribution curves, the usual method of obtaining the mean or median was inaccurate, and was not used; instead the mean (also the median), calculated on the assumption of a normal distribution, was used to locate the center point of each distribution and proved satisfactory. The effect of polarity becomes very apparent in the plate-type separator where frictional charges play a very important part when using highly resistive minerals such as zircon. With rutile, a comparatively conductive mineral, polarity of the electrode has little effect. On the other hand, the magnitude of the voltage has a far greater effect on conductive than on resistive minerals. Shiou-Chuan Sun (authors' reply)—Thanks are extended to Drs. Ralston and Fraas for their keen interest in this paper. Their questions concerning coal dust,

Jan 1, 1951

By E. A. Steigerwald, G. L. Hanna

The influence of work-hardening exponent on the variation of fracture toughness with material thickness was studied for high-strength steel, aluminum, and titanium alloys. The results indicate that, when materials are compared at similar fracture toughness to yield strength ratios, the material with the lower work-hardening exponent undergoes the transition from flat to slant fracture at a larger thickness than material with a high work-hardening exponent. In the thickness range where complete slant fracture is obtained the reverse is true and a lower work-hardening exponent results in a lower fracture toughness. The influence of work-hardening exponent on fracture toughness is, therefore, dependent on the particular fracture mode. In the transition region a low work-hardening exponent is beneficial for fracture toughness while in the 100 pct slant region it is detrimental. THROUGH the use of fracture mechanics analyses, the influence of geometric variables on the crack propagation resistance of structures can be interpreted with reasonable consistency. However, in order to gain a more complete understanding of the fracture process, the influence of material parameters on crack propagation must be defined and coupled to the macroscopic fracture mechanics approach. The work-hardening exponent, which characterizes specific material behavior, may serve as an effective parameter to allow some degree of coupling to be accomplished. In the extension of a crack in a specimen of suitable dimensions the propagation process occurs in a stable manner when the crack extension force is balanced by the resistance to crack extension, which exists in the material at the crack tip. As the applied stress, and therefore the crack extension force, on the specimen increases, the resistance also increases primarily because the effective plastic zone at the crack tip, which is the main energy absorption process, becomes larger. Since the work-hardening rate of a material influences the stress-strain relationship, it will also influence the energy absorption process in the plastic enclave at the crack tip and hence should have an effect on crack propagation. A number of studies have been made correlating the strain-hardening exponent or the strain to tensile instability with the ability of a material to resist fracture. Gensamer1 concluded that a low-strain-hardening exponent would result in a steep strain gradient at the base of a notch. He reasoned that a large work-hardening coefficient would result in high-energy ab- sorption due to the increased area under the stress-strain curve. Larson and Nunes2 experimentally observed in Charpy tests on steels heat-treated to below 200,000 psi yield strength that the energy to failure in the fibrous mode, i.e., above the brittle-to-ductile transition temperature, was logarithmically related to the strain-hardening exponent. In order to avoid the complicating effects present in studying materials which undergo a brittle-to-ductile transition, Ripling evaluated the notch sensitivity of a variety of fcc metals with varying work-hardening exponents.3 The results indicated that the relative notch sensitivity, as determined from tests on specimens with a sharp notch, decreased with increasing values of strain hardening. Although the energy required for ductile or fibrous fracture increases with increasing work hardening, high-strength steels often exhibit improved crack propagation resistance when heat-treated to obtain low values of strain hardening.4,5 An analysis of whether low strain hardening is beneficial or detrimental to crack propagation resistance must depend on the particular fracture criterion involved. At temperatures where the material is relatively ductile and the development of a critical strain is required for fracture, high strain hardening increases the energy required to produce failure. In the transition region and below, however, a critical stress law appears to be valid6 and a low rate of work hardening may produce superior resistance to semibrittle crack propagation. The experimental program is aimed at studying these possibilities and determining the specific influence of strain hardening on the crack propagation resistance of several high-strength materials. MATERIALS AND PROCEDURE The alloys, chosen as representative of various classes of high-strength materials, are summarized in Table I. The heat treatments evaluated along with the smooth tensile properties are presented in Table 11. Pin-loaded sheet tensile specimens were employed to determine the smooth tensile properties. A strain gage extensometer (measuring range 0.200 in.) was used at a strain rate of 0.02 in. per in. per min. The work-hardening exponents were determined from the stress-strain curves generated in the smooth tensile tests and the assumption that the portion of the stress-strain curve beyond the yield point can be described by the power relationship: where a is the true stress, P is the true plastic strain,

Jan 1, 1969

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of' analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,' the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS' A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By H. L. Bilhartz, H. F. Dunlap, C. R. Bailey, Ellis Shuler

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent 'saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge's paper.' In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01' the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949

By C. R. Bailey, H. F. Dunlap, Ellis Shuler, H. L. Bilhartz

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent 'saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge's paper.' In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01' the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949

By Reaves. M. J.

The title of my talk, "What Happened to the Uranium Boom?" is old news. Certainly it is for this group. All of us that make our living in uranium know that the boom of the last half of the 1970's is over. U.S. production has been exceeding consumption by more than two to one. Mines and mills are closing and yellowcake prices have been dropping for over 20 months. The gloomy outlook for the industry in the near term has been well documented by soothsayers of various descriptions, your daily newspapers, and in the Nuexco Monthly Reports. I'd like to attempt to describe the next upturn in the market (speculate, really) based upon the clues we're seeing now. In order to do that, I'd first like to go over briefly, some of the market factors that contributed to the recent price drop and resultant production cutbacks, and then hypothesize on the way these factors are changing and will change. Market prices are greatly affected (maybe even entirely determined) by buyer perceptions. This is particularly true with uranium, because of the long lead times associated with nuclear plant construction and also with conventional mine/mill development. Before the price rise (say, 1975) utility uranium buyers believed that: 1) U.S. producers would have difficulty expanding to meet U.S. demand. 2) Australian and Canadian production was essential to avoid shortages in the early 1980's. 3) Uranlum prices would continue to rise as demand exceeded supply. 4) Enrichment capacity would become inadequate. It was thought necessary, therefore, to build enriched inventory in the early 1980's for use in the late 1980's. Artificially accelerated expansion of the uranium producer industry was necessary to accommodate anticipated enrichment demand. Current perceptions are largely the opposite. These are the beliefs that were held most of this year and late last year as prices dropped. 1) U.S. production is far in excess of domestic need. Contraction of the U.S. production lndustry is necessary. 2) Canadian and Australian supply is optional and not essential. Producers in those countries are expanding mainly by displacing higher cost production and not because they fill a void, 3) Prices may be essentially stable for some time. 4) Enriched uranium is in excess supply. That is 1981. 1982 is shaping up to look like this: 1) Prices will have bottomed out. (That is not Nuexco's opinion necessarily, by the way, but it is my opinion.) 2) There will still be substantial utility inventories, but fewer spot sales. 3) Canadian and perhaps Australian sellers will have made substantial sales in the U.S. and will be aggressively seeking more. 4) U.S. production will have been dramatically curtailed. U.S. utilities that wish to con- tract long term will have difficulty in finding domestic sellers. Concern will develop about the availability of U.S. production capability. Virtually all long term con- tracts signed will be with non-U.S. sellers. 5) An awareness will begin to develop among U.S. buyers that we are approaching a period of dependence upon foreign uranium (which will be true). The history of the uranium market has been one of dramatic changes and overreaction to those changes. The rapid price rise of a few years ago generated excess U.S. production capacity and the rapid price drop of the last two years will almost certainly result in too little capacity. It will soon be difficult for U.S. buyers to buy domestic material except on the spot market. The question is, "will they care?" The lack of demand, of course, is the underlying reason for the current poor health of the uranium industry. In 1972, 1973 and 1974 collectively, there were 105 nuclear reactors ordered in the U.S. That ordering rate was expected to continue and accelerate throughout this century. In 1975, 1976, 1977, 1978, 1979, and 1980 altogether, there were 56 more reactors cancelled than ordered. The net growth of our only customer since 1974 has been a negative 56. TO put this in perspective, if these 56 reactors were operating now it would more than double present U.S. uranium consumption. Underlying lack of demand is something that is simply not going to change in this decade. Time is going to be required. The NRC indicates that the maximum feasible number of new reactors that can be licensed each year is six. That would increase uranium consumption by only 10% per year. New reactors, if ordered tomorrow, would not generate new uranium demand until after 1990. Even so, United States' consumption of uranium will rise from the 1980 level of 18 million pounds per year, to

Jan 1, 1982

By N. S. Stoloff, K. R. Jordan

The temperatwe and grain size dependence of the mechanical avoperties of ordered and disordered Fe-49 pct Co-2 Pct V were investigated. The yield and flow stresses obeyed the Hall-Petch relationship u = ai + kd-&apos;I2. Ohdering reduced the intercept stress cjj and raised the Petch slope, k, at all temperatures. Ordering also increased the temperatwe dependence of k. The ductile to brittle transition temperature increased with order and grair~ size. Cleavage fracture was nucleation limited and the fracture stress did not zlary linearly with d-&apos;". A quantitative test of the Cottrell-Petch fracture theory (and recent modifications which consider the influence of slip mode), demonstvated that this theory is not applicable to FeCo-V. COTTRELL&apos; and etch&apos; independently suggested that a criterion for cleavage failure at the yield point, a,, based on dislocation pileups at a grain boundary or other obstacle to dislocat.ion motion, is: aYYkd&apos;I2 1 opy [ll or, equivalently, aikz,d112 +k:)bpy [2] where a, and ky are the Hall-Petch intercept and slope, respectively, 2d is the grain diameter, P is a geometric factor dependent on the macroscopic ratio between shear and tensile stress, p is the shear modulus, and y is the true elastic surface energy. When the product of quantities on the left side of the equation is equal to or exceeds that on the right, cracks should be able to nucleate and propagate at the yield stress, as shown schematically in Fig. 1. Therefore a high intercept stress, high Petch slope, or coarse grain size favors brittleness. petch3 associated the existence of a ductile to brittle transition in ferrous alloys with the temperature dependence of ai. One of the earliest modifications of the Cottrell-Petch theory was presented by ~rmstrong,~ who derived an expression for transition temperature in terms of several measurable flow and fracture parameters. The latter paper was able to rationalize situations in which the transition temperature increases with decl-easing grain size, as in the case of molybdenum,&apos; and also suggested that Ppy should be a function of grain size as well as temperature. More recently Johnston et a1.6 and Smith and worthington7 have suggested that the temperature or composition dependence ol&apos; ky must also be taken into account if there is any cha.nge in deformation mode, as from wavy to planar slip, or wavy slip to twinning, with change in temperature or solute content. Armstrong %as suggested that for hcp metals changes in o;k,dw> o;k,d1/2< / is / ^^^^ / / y_______________________________________ d-"2 Fig. l—Schematic representation of grain size dependence of yield stress, cry, and fracture stress, CTF. Intersection defined by Cottrell-Petch equation. slip mode should be incorporated in the theory through changes in the critical resolved shear stress for the slip system which controls ky. The purpose of the present investigation was to critically test the modified677 Cottrell-Petch theory of fracture in the superlattice alloy Fe-49 pct Co-2 pct V, by studying the grain size dependence of the yield and fracture stresses over a range of temperatures, in conjunction with an investigation of slip mode and fracture behavior. Previous work has shown that long range order results in a sharp decrease in flow stress, a small increase in work hardening rate and a drastic upward shift in the ductile-brittle transition temperature of F~CO-V.~&apos;~ The only comprehensive study of slip character in this alloy has been reported in a preliminary account of the present investigation.10 EXPERIMENTAL PROCEDURE The experimental work was carried out on material produced from a 10 lb vacuum melted ingot, of composition 49.32 wt pct Co, 2.09 wt pct V, balance Fe. 30-mil thick sheet samples with a 1; in. gage section were machined from cold rolled stock. The degree of cold work ranged from 85 pct for the finest grained samples to 5 pct for the coarsest grain size. Details of ingot fabrication are reported elsewhere." Equi-axed grain sizes in the range 12.7 to 75.4 p were obtained by annealing for varying times at 850°C. (Re-crystallization annealing time, rather than temperature , was varied to control grain size to insure that samples of all grain sizes contained equivalent quenched-in vacancy and interstitial concentrations.) Grain sizes were measured by the line intercept method on several specimens of each grain size. Following recrystallization, all samples were disordered by quenching into iced brine.

Jan 1, 1970

By C. R. Barrett, N. N. Singh Deo

The high-temperature steady-state creep behavior of a series of dilute copper-silicon alloys was studied to determine the effect of stacking fault energy on the creep-rate. The steady-state creep rate is, when taken at equivalent diffusivities decreases with decreasing stacking fault energy. The stress and temperature dependencies of is suggest that creep is a difusion controlled dislocation climb process. Electron microscopy studies of the creep substructure revealed: 1) the subgrain size is not a function of the stacking fault energy in these alloys, 2) the dislocation density not attributed to the subgrain walls seems to be higher during primary creep and decreases to a lower steady value during steady-state creep, and 3) the dislocation density during steady-state creep decreases with decreasing stacking fault energy. In the past few years numerous investigators have studied the influence of stacking fault energy on high-temperature creep strength. Most of these investigators have confined their attentions to studying the relationship between steady-state creep rate, is, and stacking fault energy, ?, when samples are tested under conditions of comparable stress and temperature. For the case of fcc metals, it was initially shown by Barrett and Sherbyl and since confirmed by many others2"4 that is decreases with decreasing ?, often following an empirical relation of the form i ?m where m is a constant about equal to 3. The application of theory to explain this observation has not been entirely successful. One of the main difficulties has been the almost complete lack of structural information (dislocation density, subgrain size, and so forth) for samples with different stacking fault energies, tested under high-temperature creep conditions. weertman5 has attempted to explain the stacking fault energy dependence of is on the basis of a dislocation climb mechanism. Assuming that both the rate of dislocation core diffusion and the ease of athermal jog formation decreases as ? decreases Weertman has argued that the rate of dislocation climb and hence the creep rate should also decrease as ? decreases. One questionable aspect of Weertman&apos;s analysis is the assumption that core diffusion down extended dislocations is slower than core diffusion down unextended dislocations. The only experimental work done in this area, by Birnbaum et al.6 on nickel and Ni-60 Co, has shown the core diffusivity to increase with decreasing ?. Theories of steady-state creep based on the diffusive motion of jogged screw dislocations often seem unable to predict even the qualitative nature of the es- relationship. Assuming that Weertman is correct in his assumption that the dislocation jog density decreases with decreasing ? then the jogged screw theories predict an increasing dislocation velocity with lower ?. It is usually assumed that the increase in dislocation velocity implies a corresponding increase in creep rate. However, two other factors must be considered before such a statement can be made. That is, we must know how both the mobile dislocation density and the effective stress (the difference between applied stress and internal stress) vary with ?. Significant changes in either one of these factors could outweigh any change in dislocation velocity accompanying a change in ?. And with the slower rates of recovery expected in low stacking fault energy materials it seems likely to expect both mobile dislocation density and effective stress to be dependent on ?. Sherby and Burke7 have suggested that stacking fault energy influences the creep rate in an indirect way. These authors cite evidence that the steady-state subgrain size generated during high-temperature creep is a function of ? decreasing with decreasing ?. Assuming the creep rate to be proportional to the area swept out by each expanding dislocation loop and that subgrain boundaries are good barriers to dislocations, then the creep rate should be proportional to subgrain area, hence increasing as ? increases. A critical evaluation of any of the above theories requires more quantitative information concerning the dislocation substructure generated during high-temperature creep. Accordingly this investigation was undertaken with an aim of studying the influence of stacking fault energy on tbe steady-state creep characteristics of a series of dilute copper-silicon alloys. Special emphasis was placed on studying the strain dependence of both the dislocation configuration and density. MATERIALS AND PROCEDURE Dilute copper-silicon alloys of the compositions shown in Table I were tested in tension at constant stress. The relative stacking fault energy of these alloys has been determined and is shown in Table 11. An Andrade-Chalmers lever arm was used to maintain constant stress and testing was carried out in a water

Jan 1, 1970

By J. P. Zannaras

If we assume that testing of the model started at time t1, that time t2 was the instant at which the elastic limit of the material was passed at the points of the maximum stress, and that at time t3 the failure of the model was completed as shown in the typical photograph (Fig. I), then actually the photograph shows the final results of what took place between time t2 and t3. By the principle of similitude all conclusions drawn from the behavior of the model were applicable and valid for actual mine roofs up to the time t2 after time t2 motions and friction came into play during the destruction of the model. The events between t2 and t3 and the photograph itself are not representative of the events expected in an actual mine roof unless corrections imposed by the principle of similitude are made. It can therefore be stated that all conclusions and observations of the author from the photographs are applicable only to his small-scale experiments and not to actual mine roofs. Without investigation of the true stresses or the combined maximum stress induced in the beds it has been assumed by the author that failure occurred solely due to bending stress caused by loading of the beds. (The author states that D was taken to be the theoretical strain given by elementary beam theory.) Fig. 1 shows that the beds were clamped together. This clamping was necessary to prevent slipping of the beds due to the horizontal shear. However, this clamping caused an uncontrolled and undertermined com-pressive stress S at the end of the beds, and this com-pressive stress caused a true tensile stress ?S (? PoiS-son ratio). This true tensile stress combined with the tensile stress produced at the end of the beds due to loading (fixed beam uniformly loaded), and the horizontal shear which is maximum at the end appears to be the most probable maximum stress produced in the beds. It is therefore evident that the author in performing this experiment has introduced stresses in the model not existing or dissimilar to actual mine roofs, and therefore his conclusions may be applicable to his small-scale experiments but inapplicable to actual mine roofs. Louis A. Panek (author&apos;s reply)—The discusser&apos;s difficulty is related to mechanics of materials rather than similitude. The effect of time did not enter into the tests in any way, being simply excluded from consideration in this study, because all quantitative results entering into the design equations are based on measured (between time t1 and time t2) bending strains that are well below the breaking strain (i.e., in the elastic range) for the model material. Time does not become a significant factor until the rock stress reaches 80 to 90 pct of the breaking stress." The objective of this investigation was not to predict that bolted roof will fail after time t, but was instead to develop a safe roof, that is, roof in which the bending strain is much less than (say less than 50 pct of) the breaking strain. The models tested to failure had no direct bearing on the design equations. Although for some rocks time may influence the magnitude of stress or strain at which fracture occurs, breaking stress or breaking strain values were not employed for any purpose in this investigation. Tests to failure were made only to obtain additional evidence regarding the behavior of the bolted laminae&apos; as evinced by the locations of the cracks. As stated in the last paragraph of the paper, if one wishes to predict the time or stress conditions for which the roof will fail, additional information is required. The reason for clamping the laminae is to make them behave liked clamped beams, which closely approximate the clamped-plate condition of the actual mine roof beds (Ref. 5, p. 1; Ref. 6). The writer has previously demonstrated that the bending stresses induced by centrifugal loading in a clamped model beam are in agreement with those predicted by theory;&apos; hence clamping has no significant effect on the bending ,trains measured during a test. Moreover, actual ,in, roof beds are likewise subject to a clamping effect due to weight of superincumbent strata carried by the pillars or ribs on each side of the opening. It is emphasized that this study was restricted to evaluating only the reinforcing effect produced by the bolts. Procedures employed in the experiments and in the data analysis were such as to deliberately exclude the effects of other factors. The objections offered are therefore invalid,

Jan 1, 1957

By Michael Epstein, Daniel E. Rosner

Fume nucleation sufficiently close to vaporizing suvfaces can augment net vaporization rates into cooler environments. Environmental conditions favoring large vaporization rate enhancements are briefly discussed and a previous theoretical treatment of this nucleation phenomenon is generalized to account for the self-regulating effect of condensalion-heat release within the boundary layer. Despite kinetic limitations on homogeneous nucleation, and latent heat release, non-diffusive condensate removal processes appear to make possible large enhancements in steady-state vaporization rates, provided surface temperatures are well below the boiling point. When condensed phases vaporize (or dissolve) into cooler media, the diffusion-limited mass loss rate can be strongly influenced by the process of nucleation/con-densation (or precipitation) within the thermal boundary layer. This condensation process (which typically leads to mists or fumes in the case of evaporation into cooler gases) has the effect of steepening the vapor pressure profiles near the evaporating surface, since the condensation zone acts as a vapor sink. However. the resulting enhancement in the diffusion-limited evaporation rate can be estimated (as first done by Turkdogan1 for the case of molten iron/nickel alloys evaporating into helium) only if one has independent knowledge of the critical supersaturation, sCrit(T), required to homogeneously nucleate the vapor.* In a recent reformulation and generalization of the theoretical model of Ref. 1 it has been shown that, when log sCrit is approximately linear in reciprocal temperature, rather simple expressions can be derived4 for the ratio of the actual rate of vaporization j" to either the minimum (no condensation) rate j"min, or the maximum (equilibrium condensation) rate j"max In the present communication we wish to briefly report on further developments and implications of the formulation of Ref. 4, with emphasis on i) environmental conditions favoring large enhancements in vaporization rate, and ii) the self-regulatory influence of condensation heat release (neglected in Refs. 1 to 4) on predicted vaporization rates. Additionally, we take this opportunity to correct several misprints appear- ing in Ref. 4, and comment on Elenbaas&apos;s recent criticism5 of Ref. 1. MAXIMUM POSSIBLE VAPORIZATION RATE IN PRESENCE OF CONDENSATION A nonequilibrium theory is of interest because of the very large difference between the minimum (no condensation) and maximum (equilibrium condensation) vaporization rate. The magnitude of this maximum possible enhancement can be shown quite clearly by combining a result of Refs. 3 and 4 with the fact that for most liquids there is a simple relationship between the molar heat of evaporation, A, and its boiling point, i.e., A/(RTBp) = C, where the constant C, often called the Trouton ratio, takes on values not very different from 11.* More generally, for any substance (including The Trouton ratio (which for water is 13, for methane, 10, and so forth) will be recognized as the ratio of the molar entropy change upon vaporization (at TBP or Ttransf) to the unlversal gas constant R. Its near constancy reflects the fact that the change in atomic order upon vaporization depends only weakly on the kinds of molecules involved. those that sublime under ordinary conditions) we can define a characteristic transformation temperature. Ttransf, by a relation of the form Ttransf =A/(CR), and then examine the maximum possible evaporation rates as a function of how far removed from Ttransf are the surface temperature, Tw, and ambient temperature, T. Subject to the assumptions: 1) equilibrium vapor pressure, pv,eq, everywhere small compared to prevailing total pressure, p, and 2) negligible effect of condensation heat on temperature profile, the maximum enhancement ratio was found (Eq. [17], Ref. 4) to be: where, for most vapors, Nu/NuD (the ratio of heat transfer coefficient to mass transfer coefficient for the same configuration) is a number near unity.* Ex- *An alternative derivation of the Nu = NuD special case of this equation. revealing its validity for arbitrary velocity/temperature profiles in a laminar boundary layer, is given in Ref. 3. amining this result for a "Trouton substance", one obtains the results shown in Fig. 1, constructed for C = 11. Since we are concerned with vaporization enhancements (j&apos;max/J"min > 1) at surface temperatures below Ttransf, this area of interest is shown unshaded. One notes that at a fixed ambient temperature (hence, T/TtranSf) there is a unique surface temperature, 2T , at which j"max/j"min attains its peak value; moreover, the peak enhancement ratio, see dashed locus. Fig. 1, is: (NuA/NuD)(C/4)(Ttransf/T,). Hence, if Nu = NuD, when the ambient temperature is less than 1/4 of TtranSf the peak enhancement exceeds the Trouton

Jan 1, 1969

By D. A. Kraai, S. Floreen

The effect of 1 to 50 ppm S on the ductility of nickel at 800° to 1400°F was studied. Results at each temperature showed a decrease in the reduction of area from approximately 95 to 5 pet over the sulfur range studied. Ductility varied with grain size, but only to a minor extent relative to the sulfiw effect. The effects of sulfur were completely offset by the addition of small amounts of magnesium. The results indicate that the "hot-short" loss in ductility is not an inherent property of nickel. Some possible mechanisms which cause the loss in ductility are described. MANY metals or alloys that normally possess high ductility exhibit a ductility loss at intermediate temperatures. This loss in ductility is often called "hot-shortness". Numerous examples of this phenomenon have been reported in the literature. Much of this work has been reviewed by McLean1 and by Rhines and Wray.2 To date there is no fully satisfactory explanation of the cause of this intermediate-temperature hot-shortness. It is generally recognized that impurities, and particularly impurities that form low-melting phases, can cause embrittlement. Examples of hot-shortness have been reported, however, where there were no obvious impurities present which would lower the ductility. Thus there has been some basis for believing that hot-shortness is an inherent property, and that even the purest metal would display a hot-short loss in ductility. This latter hypothesis was recently put forward by Rhines and wray2 based on studies of nickel and nickel alloys. In the discussion of this paper, however, Guard noted that high-purity nickel showed no hot-shortness.3 Thus there is reason to doubt whether pure nickel, or by inference any other pure metal, will inherently exhibit hot-shortness. The present work was initiated to determine the extent to which hot ductility was sensitive to very small amounts of an impurity element. If it could be demonstrated that hot-shortness could be induced by only minor amounts of an impurity, then it might be argued that hot-shortness in general is an impurity effect, and not a fundamental property of pure metals. The particular impurity studied was sulfur in nickel. The deleterious effects of sulfur are well- known. It is also well-known, and will be shown below, that additions of magnesium will render sulfur innocuous. When no such refining agents are added, however, the Ni-S system is a very useful one for studying the influence of small amounts of impurities. EXPERIMENTAL PROCEDURE Two heats containing -24 ppm S were vacuum-melted and small amounts of magnesium were then added under an argon atmosphere. These alloys were used to show the effectiveness of the normal magnesium treatment in overcoming the influence of sulfur. A second series of alloys with a sulfur range of 1 to 50 ppm was then prepared by vacuum melting nickel in alumina crucibles. No elements, such as magnesium, which tend to combine with sulfur were added. The higher sulfur contents were attained by adding nickel sulfide. Lower sulfur contents were prepared using a method in which the melt was oxidized under vacuum to produce the reaction S + 2O = SO2 These heats were subsequently deoxidized with carbon. Ten- to twenty-pound ingots were cast of all of the alloys studied. The compositions are given in Table I. The ingots were forged and hot-rolled to 3/4-in. bar. They were then annealed at either 2000" or 1600°F to produce different grain sizes. One-quarter-in.-diam tensile specimens were machined from the bars. These were tested at 800°, 1000o, 1200°, and 1400°F. The specimens were held at temperature approximately 45 min before testing. The strain rates were 0.005 min-1 to yielding, and 0.05 min-&apos; after yielding. No extensometers or gage marks were placed on the specimens because the higher sulfur heats tended to fracture at the knife-edge indentations or gage marks. The properties measured were ultimate tensile strength and reduction of area. The analytical technique for determining sulfur at low levels was that developed by Burke and Davis.4 They reported a standard deviation of 1 ppm at an average sulfur level of 4 ppm in NBS standards. A standard deviation of 3 ppm is probably more realistic for the alloys used in this investigation considering the possibility of some segregation in the ingots. RESULTS A summary of the tensile results is given in Table I. As shown in the table, both heats to which

Jan 1, 1964

By Shiou-Chuan Sun

THE presence of an excessive amount of tough froth in the flotation of minerals, particularly coals, may create trouble in dewatering, filtering, and handling. Froth is also a nuisance in many chemical industries.&apos; This paper presents a study on the destruction of extremely tough froths with intense high-frequency sound. The data indicate that sound waves can be employed for continuous atandsoundwavescan instantaneous defrothing. A powerful high-frequency siren was used in obtaining the data. Also tested was an ultrasonorator of the crystal type with a frequency range of 400, 700, 1000, and 1500 kc per sec and a maximum power output from its amplifier of 198 w. The results, not presented, indicate that as now designed this machine is not suitable for defrothing. Although the sound generators of the magnetostriction type2,3 and of the electromagnetic type&apos;.&apos; were not available, it is beelectromagneticlieved they are capable of producing the required sound intensity for defrothing. The use of ultrasonics for defrothing was suggested by Ross and McBain1 in 1944. Ramsey8 reported in 1948 that E. H. Rose mentioned a supersonic device that broke down flotation froth but with low capacity. The writer has not been able to find any published literature containing practical experiments. Theoretical Considerations The mechanism of defrothing by sound is attributed to the periodically collapsing force of the propagated sound waves and the induced resonant vibration of the bubbles. The collapse of froth is further facilitated by the sonic wind and the heat of the siren. Sound waves can exert a radiation pressure&apos;," against any obstacle upon which they impinge. When a froth surface is subjected to the periodic puncturing of sound waves, the bubbles are broken. According to Rayleigh9 and Bergmann,12 the radiation pressure of sound, P, in dynes per sq cm is given as: P = 1/2 (r+1)i/v where r is the ratio of the specific heats of the medium through which sound is traveling and is equal to 1 on the basis of Boyle&apos;s law; i is the sound intensity in ergs per sec per sq cm, and v is the sound velocity in cm per sec. In this case, the accuracy of the formula is only approximate, because a perfect reflection can hardly result from a column of froth. In addition to the radiation pressure, the propagated sound waves cause the bubbles of the froth to have a resonant vibration.&apos;" he vibratory motion of the bubbles causes collision and coalescence, thereby weakening if not breaking the bubble walls. Sonic wind and heat were also generated." The sonic wind can exert pressure on the froth surface, and the heat can evaporate the moisture content of the bubble walls as well as expand the enclosed air. Apparatus The defrothing apparatus, shown in Figs. 1 and 2, consists of a powerful high-frequency siren, a glass or stainless steel beaker of 2-liter capacity with 12.4 cm diam and 17.1 cm height, and a metal reflector. The beaker was placed 2 in. above the top point of the siren. The metal reflector was adjusted to reflect and focus the generated sound waves into the central part of the beaker. Fig. 2 shows the crystal probe microphone used to measure the acoustic intensity and the mandler bacteriological filter employed to introduce compressed air into the beaker for frothing. The apparatus was enclosed in a soundproof cabinet equipped with a glass window. The siren, shown in Fig. 3, consists of a rotor that interrupts the flow of air through the orifices in a stator. The rotor, a 6-in. diam disk with 100 equally spaced slots, is driven by a 2/3 hp, Dumore W2 motor at 133 rps. The frequency of the siren can be varied from 3 to 34 kc. The maximum chamber pressure is about 2 atm, yielding acoustic outputs of approximately 2 kw at an efficiency of about 20 pct. The siren itself is relatively small and can be operated in any orientation. A detailed description of the siren has been given by Allen and Rudnick.11 Collapse of Froth To study the sequence of the collapse of froth, the glass beaker was partially filled with 920 cc water, 100 g of —150 mesh bituminous coal, 0.3 cc petroleum light oil, 0.2 cc pine oil and 1.54 cc Pyrene foam compound. This mineral pulp was agitated for 5 min and then aerated through a mandler filter until the empty space of the beaker, approximately 9 cm high, was filled completely with min-

Jan 1, 1952

EXPLORATION U.S. 4,065,972 - Exploration for subsurface ore bodies of uranium. mercury or other inorganic or organic minerals having specific gases associated thereto Small gas sample containers are planted in a plurality of shallow holes in the surface of the earth in a predetermined pattern and left in place for a period of time sufficient to collect migrating gases. Each container includes a gas collection chamber and means for admitting gases at a predetermined flow rate. Strips of detector material which is sensitive to specific gases are mounted in the collection chamber. Recovered containers are subjected to qualitative and quantitative analysis. F. W Holub and H. W. Alter, assigned to Terradex Corp Jan. 3, 1978. 9 pp (73-421 5R) Filed 5-24-76 (689,710) Same. British 1,498,737, dated Jan. 25, 1978

Jan 1, 1979

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3&apos;= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker&apos;s experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By P. A. Beck, M. V. Nevitt

All binary and a number of ternary u alloys formed by first long period transition elements were examined and found to be ferromagnetic at low temperatures. The Curie temperatures for these alloys were measured. It was found that the correlation of the Curie temperature with composition may be described qualitatively in terms of the contributions of the various component atomic moments to the saturation moment of the alloy. Ternary Fe-Cr-Mo u phase alloys were also found to be ferromagnetic, with a Curie temperature dependent on the iron content and largely independent of the unit cell dimensions. Similar relations were found for the Co-Fe-Cr and the Co-Cr-Mo a alloys, where the Co + Fe content appears to determine the Curie temperature. RECENTLY, it has become increasingly evident that the u phase is some kind of an "electron compound." Several papers1-&apos; discussed the empirical correlation between the composition of the various u phases in alloys of the transition elements and the distribution of electrons in the partially filled d-levels of the component atoms. However, a picture of the latter can be formed only in a more or less intuitive manner, as in the Pauling theory," and the rigorous treatment of these problems is at present prevented by lack of adequate knowledge of the electronic structure of the transition elements in the metallic state. It appeared reasonable to expect that investigation of the magnetic properties, which are related to d-shell electrons, may help in clarifying the physical nature of the foregoing empirical correlation. Qualitative tests of samples of various compositions have shown that certain u alloys become ferromagnetic at liquid nitrogen temperature." The present investigation was undertaken to determine whether or not low temperature ferromagnetism is characteristic of a large variety of u alloys and to establish how the Curie temperatures of ferromagnetic u alloys are influenced by changes in composition and in lattice parameter. In the first portion of the in- vestigation, Curie temperatures were measured for a series of u alloys containing either vanadium or chromium with one or two of the elements manganese, iron, cobalt, or nickel. In the second phase of the work, data were obtained on the Curie temperature of ternary (Fe, Co, Cr)a, (Fe, Cr, Mo)a, and (Co, Cr, MO)U alloys, as a function of composition and of interatomic spacing. Experimental Procedures High frequency vacuum melting in high purity re-crystallized alumina crucibles was employed in the preparation of the u alloys, using metals whose lot analyses are given in Table I. Approximately two-thirds of the alloys were analyzed chemically, the analytical results being in acceptable agreement with the intended compositions, as seen in Tables I1 and 111. The specimens were annealed for homogen-ization in an atmosphere of purified 92 pct He and 8 pct H, mixture or in evacuated and sealed Vycor tubes at temperatures from 780" to 1300°C, depending on the temperature range of the u phase field for the particular composition. The annealing temwerature and time for kach alloy are given in Tables 11 and 111. Curie points were determined by an induction method; the change with temperature of mutual inductance between two coils was observed when the i-u specimen was inserted into the flux path between the coils. The transformer consisted of three coils each containing 1200 turns of 0.0050 in. diam enameled copper wire. The center coil, P in Fig. 1, served as the primary coil, and was linked magnetically with each of the two secondary coils, S, and S? which were connected in series opposition. The primary coil, P, was energized by an audio-oscillator, set at a frequency of 500 cycles per sec, while the signal from the transformer secondary circuit,

Jan 1, 1956

LIST OF MEMBERS AND ASSOCIATES ARRANGED ACCORDING TO STATES AND TOWNS ALABAMA Aldrich, Aldrich, W F Anniston, Noble, A E, Smith, N B Aibacoche, Bradley, D II Bessemer, Fergusson, V Birmingham, Aldrich, T H, Aldrich, T H, Jr, Bowron, J, Bowron, C E, Davis, F H, Dimmick, F D, Hillman, McCarthy, M E , McCormack, McCrery, Ramsay, E, Shook, A M Bridge¬port, Wheeler, S K Ensley, McDonald, S, Shook, J W Fanbanks, Hamil¬ton, A L Helena, Squire, J Huntsville, Moss Lehigh, Toulmin Oxmoor, Green¬amyer, A G Plasma, Gage Rock Run, Garvin Sheffileld, Miller, D I Tuscaloesa, Lodge, J University, McCalley Woodward, Bukofzer, Woodward, A H ALASKA Dawson, Buck Douglas Island, Corbus, J P , Macdonald, J Hames, Le Wald, E A Jualin, Hoggatt, W B Juneau, Denby, Gaifield, Garside, Hamp¬ton, W H Rodman Bay, Phillpots Snettisham, Tisdale Sumdum, Thane Tel¬ler, Hirshberg, M R Treadwell City, Batcheller, J H , Kinzie Valdez, Esterly, G M Yukon, Dawson, Elmer, J M ARIZONA Bisbee, Clark, G C, Coombs, H L , Douglas, W, Hoatson, Parnall, S A, Pelton, R T, Ricketts, L D, Sherman, G F G, Smith, F W, Smith, H A Black Diamond, Bagge Blanchard, Cummins, Murray, J J Casa Grande, Rich¬mond, A B Clifton, Colquhoun, Grabill, Murray, H T , Plater, Smith, J D A, Veitch, Watson, W S Congress, Goodloe Crown King, Alexander, G E Douglas, Cornell, Kraemer, E L, Lee, G B, Rutherford, F Globe, Berray, Hoar, Snell Harrisburg, Smith, F C Jerome, Clark, W A, Thomas, C A Kingman, Treadwell, Wallace, J P Kirkland, Bretherton, G K Kofa, Lamp¬shire, J O , Pomeroy, H G Mayer, Haggott, E A Metca j, Blumenkranz, M , Forbes, D L H Morenca, Clark, C D, Fleming, J B, Honey man, Mills, C E, Wallace, L R Morristown, Stevens, H W Nogales, Glove, H G, Sandoval, A , Sandoval, P Octave, Rose, G W Phoenix, Armstrong, T , Butler, C E, Defty, Lindsay, L Prescott, Blauvelt, H , Bunker, C E, Claypool, W M , Drescher, F M , Fairbank, Nissen Tombstone, Gage, Poindexter, C L , Staunton, Walker, E W Troy, Cutting Tucson, Blake, W P, Burgess, De Lashmutt, I, McCleary, Mann, Prout, J W , Jr ARKANSAS Fayetteville, Purdue Fort Smith, Bache, F , Denman, H Little Rock, Fordyce, Scholz CALIFORNIA Alameda, Arents, King, L Arnador City, Downs, Tregloan Angeles Camp, Dig¬gles, R N , Kenney, C E Antioch, Belshaw Auburn, Coe, I J Ballarat, Thorns Berkeley, Abadie,, Christy, Dozier, Hall, F F , Hersam, Landfield, Lind¬say, L , Mansfield, N T, Morley, W S , Sharwood, W J Bag Oak Flat, Dron Bodae, Hamilton, W R, Hoover, T, Hoover, T J, Jackson, B L , Nutter , E, H Bullion, Power, H T Callahan, Scott, E H Campo Seco, Baird Cartero,

Jan 1, 1910

By J. H. Henderson, T. E. Morrisson

An irvestigation has been made of the production of oil through horizontal fractures of high capacity and large radius placed at the base of producing formations. The specific aitns of the study were to (I) determine by model studies the reservoir performance when gravity drainage is the only producing mechanism, and (2) develop a method of predicting such perfortnance from commonly measured reservoir proper-ties. Although the theoretical approach tailed to develop a rigorous analytic sorution to the transient problem, it (lid lead to a practical method of predicting performance. Predictions (Ire in good agreement with rates and recoveries observed in scaled-model experinzents. Capillary effects and the influence of relative permzenbil-ity are taken into account. The experimental program was mainly concerned with the influenre of fracture radius, fracture capacily and capillary hold-up on the total recovery and the rate of recovery. Much of the experimental work was done on a triangular model which represented one-eighth of a square well pattern, so constritcted that horizontal fractures of varying radii and flow capacity could be studied. An electrolytic model was used to relate the initial production rates to fracture radius, formation thickness and the drainage radius of the well pattern. The conclusions reached as a resrtlt of the work are as follows. I. The production of oil under gravity force alone into a well-propped horizontal fracture, whose radius is of the order of hundreds of feet, is a recovery method which combines high recoveries with very acceptable production rates. 2. The mechanism is effective in "dead oil" reservoirs as well as in reservoirs which possess the energy of solution gas. 3. A method of predicting performance has been developed which gives good agreement with experimental behavior in cases of practicnl interest. Even for very thick beds and large fracture radii, where actual conditions do not conform to the assumptions made, the method gives order of magnitude predictions which would not otherwise be possible. INTRODUCTION Gravity drainage of oil from a formation which has continuous ver- tical permeability over a reasonable depth interval is a surprisingly effective method of recovery. However, for a conventional well the production rates which result from gravity drainage are so low that the economics are seldom attractive. The same formation may produce rapidly and profitably by gravity alone through a high capacity, extensive (i.e., > 100-ft radius) horizontal fracture placed near the bottom of the pay section. Fig. 1 shows a schematic diagram of the plan. Energy in the reservoir gas is not a necessary condition for this recovery process. With a sufficiently large fracture, attractive production rates will result from gravity flow alone, and the producing GOR need only be the solution GOR. It is, of course, necessary to keep the fluid level in

Discussion of the papers of FREDERICH LAIST and HAROLD W. ALDRICH, FREDERICH LAIST and F. F. FRICK, W. L. AUSTIN, and STUART CROASDALE, presented at the Salt Lake meeting, August, 1914, and printed in Bulletins No. 91 and 92, July, and August, 1914. R. C. CANBY, Wallingford, Conn. (communication to the Secretary*). -Apropos of the experimental reduction of copper from cuprous chloride by fusion with ground limestone and coke, as described by Messrs. Laist and Frick, and also proposed for use at Chuquicamata., it might be of interest to refer briefly to the experience at Argentine, Kan., in the smelting of the suboxide of copper (as produced in the Hunt and Douglas process) containing appreciable quantities of chlorides. In the Engineering and Mining Journal of June 10, 1911, I. gave some account of what had appeared to be crucial difficulties with the Hunt and Douglas process, and how the filter-press difficulty had been so rapidly overcome after my discovery of the effect of the sodium salts in the leaching solutions. I also described the effect of the cupola furnace gases upon the lime rock with which I had replaced the coke in the absorption tower, which apparently showed the presence of considerable-chlorine, clue to the imperfect conversion of the subchloride to suboxide, as well as that clue to the difficulties of washing thoroughly the suboxide with the means provided, and also to the presence of chlorides in the cement copper which was smelted With the suboxide. The fumes from the cupola, when issuing direct into the atmosphere, were very dense and white, except when a hot furnace top caused a reddish tinge due to dust. These, fumes had a peculiarly suffocating effect, so that when they were blown over into the town the population suffered the greatest actual distress, not the mere annoyance which would have been clue to a disagreeable odor. The absorption tower had been built at the instance of the city authorities to abate this nuisance, and not with the idea of making any additional metal savings. A serious feature in connection with the Argentine experience with the Hunt and Douglas process was, that it had been implicitly assumed that there could be no metal loss in the Hunt and Douglas process itself, and that all attempts to locate the ruinous copper losses which were accumulating in the metallurgical accounts were devoted to the roasting department. It is possibly unfortunate for metallurgical advance along these particular lines that just about the time of this discovery of this previously unsuspected volatilization loss, in the smelting of the suboxide, the Kansas City company made a contract with the Western Union Telegraph Co. for its supply of copper sulphate and the Hunt and Douglas

Jan 11, 1914

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941