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By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By J. E. Korski

Quebec Cartier Mining Co. operates a low-grade iron ore deposit at Lac Jeannine, Que., which is located at the extreme southwestern end of the Quebec-Labrador Trough (Fig. 1). The facilities there include one of the world's largest concentrators, a hydroelectric plant of 60,000 hp, and the modern town of Gagnon. A 191-mile railway connects the mine to the seaport situated at Port Cartier on the St. Lawrence River. The harbor in Port Cartier can accommodate both lake and large ocean- going vessels and is also the site of a major grain terminal. The concentrator in Lac Jeannine is designed to produce some 8 million tpy (tons per year) of specular hematite concentrate, containing 66% Fe, from approximately 20 million tons of crude ore. An annual stripping program of 5 to 8 million cu yd of waste rock uncovers the required ore. Approximately 100,000 tons of ore and waste are removed daily on a year-round, 24-hr-per-day basis. The open pit covers an area with maximum dimensions of 8,000 x 2,600 ft (Fig. 2). Present mining plans call for an ultimate depth of approximately 1,000 ft below original ground level. The rocks in the pit area are typical of this portion of the Grenville geological province. They consist largely of marble, quartz rock, pegmatite, iron formation, and stratigraphically older gneisses. The iron-ore formation consists of medium to coarse-grained specular hematite in a quartz host rock. The formation occurs locally in a plunging, anticlinal form. The topography in the vicinity of the mine is rolling, with maximum variations in elevation of about 400 ft. The hills are thickly wooded with birch, black spruce, and some tamarack. Lakes and muskeg areas are plentiful. Precipitation and temperature records have been kept since 1959. The annual rainfall has ranged between a low of 23 in. and a high of 42 in.

Jan 1, 1969

By S. Razi

Injection luminescence of single crystals of rare-earth-activated CdS was investigated. Crystals of CdS:Nd, CdS:Er, and CdS:Yb, grown by the vapor transport technique, were suitably etched and hetero-junctions of Cu2S-CdS were fabricated on one side of the CdS substrate by chemical reaction. The device was then heated to 200°C in an inert atmosphere for 5 min. Static V-I measurements show that at low voltages (V < 1 v) the current is controlled by the junction, while at higher voltages the bulk Properties of the CdS substrate effectively control the current. Because of the large thicknesses no negative resistance was found. Reverse breakdown voltage varied from 5 v, for junctions that were not heat-treated, to 100 v, for diodes that received the proper heat treatment. The rectification ratio, measured in the range of 2 to 10 v, varied from 300 to 3000. Capacitance- voltage measurements indicate a weak dependence of the junction capacity on applied voltage. The capacity was found to increase appreciably with room light illumination. The variation of capacitance with frequency is indicative of a p+-i-n structure. An open-circuit voltage of 0.4 v was measured under an illumination of 100 mw per sq cm. Under forward bias, the bluish-green edge emission characteristic of CdS was observed. No sharp rare earth emission line was observed, which is in contrast to our results using ZnS:Tb, where, under high-voltage excitation, the rare earth emission was dominat over the lattice emission. The absence of rare earth emission implies that either the nature of the rare earth ion is different at the het-erojunction than in the bulk or the probability of energy transfer to the rare earth ion is small. RARE earth elements are playing an increasingly important role in the Synthesis of materials for a variety of purposes, e.g., solid-state lasers, color television screens, and so forth. Interesting systems result when wide-band-gap photoconducting lattices are activated with rare earths. A study of the lumines-

Jan 1, 1969

By J. J. Frawley, W. J. Childs

PREVIOUS studies have shown that if a supercooled liquid metal was perturbed by vibration the probability of nucleation is is During a recent investi- gation to determine quantitatively the amount of energy needed to cause nucleation in a given supercooled liquid specimen, it was found that at low-energy values in the megacycle range, below the threshold energy value for cavitation, the amount of dynamic supercooling was greater than the amount of static supercooling. That is, if a specimen had a given amount of thermal supercooling under static conditions, its thermal supercooling could be increased by the addition of low-energy sound waves. The material used in this investigation was high-purity bismuth. This material was chosen because of its low melting point and the high degree of supercooling which could be easily obtained. The sound gener- ator employed in this work was a commercially built Sperry ultrasonic testing unit. This unit was equipped with a barium titanate crystal as a piezoelectric transducer. These sound waves were transmitted to the supercooled melt by a Pyrex rod, as shown in Fig. 1. The transducer was coupled to this Pyrex rod wave carrier by motor oil. The Pyrex wave carrier was approximately 1.5 ft long to prevent damage to the transducer by heat. The diameter of the Pyrex wave carrier appears to be critical. In the initial tests a wave carrier of 0.5 in. in diam was employed. However, the sound waves had no effect on the amount of dynamic supercooling. When the diameter of the wave carrier was increased to approximately the inside diameter of the Pyrex crucible, the sound waves were more effective. Approximately 200 g of metal was melted under a stannous chloride flux in a 30-ml beaker by induction heating. The temperature was recorded by a Pyrex-encapsulated chromel-alumel thermocoule which was placed in the beaker after the bismuth melted. The Pyrex wave carrier was immersed slightly below the surface of the liquid bismuth and the specimen was reheated to about 500°C. It was observed that the amount of supercooling depends on the amount of superheating the specimen receives; therefore, for meaningful results the amount of superheating was the same for all heating cycles. The specimen was allowed to cool in air and the change in temperature was continuously monitored with a potentiometric strip-chart recorder.

Jan 1, 1969

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle&apos;s work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

By E. R. Russell, N. E. Richards

The current ejyiciency of aluminum cells was derived from the metal produced over a period of time and the theoretical faradaic yield. The difference in the actual amount of aluminum in the cathode at the beginning and end of the period must be determined. The weight of aluminum in the cathode was calculated from the dilution of an added quantity of impurity metal. Use of multiple indicator metals, copper, manganese, and titanium, demonstrated that the weight of aluminum in cells can be determined to within 1 pct with routine but careful chemical analyses. Over intervals of the order of 30 days, current efficiencies reliable to within 1 pct can be obtained. INVESTIGATIONS beginning with those of Pearson and waddington ,&apos; through the most recent published work of Georgievskii,9-11 illustrate the direct relationship between the composition of the anode gas and the applicability of analysis of anode gases to the control of alumina reduction cells. McMinn12 noted the lack of an independent method for measuring cell production efficiency over the short term. There is no doubt that changes in the current efficiency are immediately reflected in the composition of anode gases. However, the accuracy of faradaic yields calculated from gas analyses depends upon the degree of interaction between primary anode gas and Carbon.6 A conventional industrial practice of obtaining long-term current efficiency for production units from mass balances and quantity of electricity is generally insensitive to the impact of planned control of any one or more of the influential reduction cell parameters such as temperature, alumina concentration, and mean interelectrode distance. Consequently, there is a real need in the aluminum industry for a procedure to obtain the absolute cell current efficiency over a short term—10 to 30 days—both for the calibration of values obtained from gas analysis6 and for evaluating the effect of controlling specific parameters in the reduction process. The amount of aluminum produced may be determined by considering the cathode pool as a reduction of an impurity metal in aluminum. Analyses over a period will show a decreasing concentration of the impurity due to the accumulation of aluminum solvent. The increase in aluminum inferred from analyses is the amount produced by the cell during the period. Combining weights of the cell aluminum in the cathode at the beginning and end of a specific period, weights of aluminum tapped and the quantity of electricity passed during the interval will yield the current efficiency. Smart,I3 Lange;4 Rempel,15 Beletskii and Mashovets,16 and winkhaus17 have used dilution techniques to determine aluminum inventory in alumina reduction cells. A technique for determining the weight of aluminum in production cells by addition of small amounts of copper to the aluminum cathode was described by smart.13 The precision in values of the aluminum reservoir through dilution of copper in the cathode ranged from about 1 to 3 pct depending upon the quantity of copper added in the range 0.2 to 0.01 wt pct, respectively. Because the method appears so direct and apparently simple, one would not anticipate difficulties in application to industrial cells. The objective of this study was to resolve this problem associated with the trace metal dilution technique for determining the amount of aluminum in a cell. The approach in evaluating trace metal dilution as a basic factor in determining the weight of aluminum in the cell reservoir, and the absolute current efficiency of the Hall-Heroult cell, was to dilute more than one trace metal in the aluminum cathode so that we could discriminate among complications arising from physical mixing, the possibility of separation of intermetallic compounds, loss of the added elements, and chemical detection. EXPERIMENTAL METHODS These experiments are not complex but require standardized procedures. The technique involves addition of the trace metals to the cathode, knowing when these metals are homogeneously distributed in the liquid cathode, timing of the sampling, employing accurate and precise analytical methods, using reliable procedures for monitoring the amount of electricity passed through the cell, and accurate weighing of aluminum removed from the cell during the particular period. More accurate results might be obtained if the increment in concentration of the added indicator metals were of the order of 0.1 to 0.2 wt pct. The method must be applicable to production units and, hence, the contamination of the aluminum minimized. For this reason, the concentration of trace metals in the cathode was kept below 0.07 wt pct and generally at 0.04 wt pct level. Trace quantities of copper, manganese, titanium, and silicon are already present in virgin aluminum and are suitable as additives from electrochemical and analytical points of view. Concentration of silicon is quite dependent upon the characteristics of the raw materials and was not used extensively in this work. Chemical Analyses. All instrumental analyses require calibration against an absolute technique such as a gravimetric, volumetric, or spectrophotometric method which represents the ultimate in sensitivity, precision, and accuracy. On review, the best methods for copper appeared to be optical absorption without

Jan 1, 1969

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,&apos; who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By T. Reed Scollon

Major interrelated factors to be considered in assessing the impact of air pollution control regulations on coal are: (I) the fuel and fuel-related limitations of such regulations; (2) the rate of adoption and areal scope of the regulations; and (3) the availability of fuels and fuel-burning equipment to meet the requirements. A growing number of regulations contain provisions limiting the emissions of sulfur oxides or the sulfur content of fuels or both. With few exceptions, these limitations have not yet become fully effective in those areas which have already adopted regulations, and pertinent details of future regulations or legislation for most other areas are unknown at this time. Sufficient information is not avail- able to determine the availability of low-sulfur fuels at various demand and price levels, and large-scale commercial feasibility of sulfur-oxides removal processes and equipment is believed to be some years away. Accordingly, with the many uncertainties and unknowns, it is possible at best to make only a rough assessment of the impact of such regulations or legislation on coal.

Jan 1, 1969

By Stanley C. Suboleski, J. Richard Lucas

Simulator I, a program to simulate production in room and pillar mining systems containing up to six face operations, was developed at Virginia Polytechnic Institute under sponsorship of the Office of Coal Research. Since its inception, several hundred analyses have been run, with over thirty companies using the program. This paper describes the simulation technique used in this program, the output achieved from an analysis, and reviews the experience gained in working with Simulator I.

Jan 1, 1969

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun&apos;ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n&apos;, and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.&apos;,~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1&apos;2&apos;5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen&apos; and others.2&apos;9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.&apos;&apos; Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

By Robert O. Vernon

Urban sprawl, and all its attendant problems, is upon us. In Florida, and much of the rest of the world, this has been intensified by a special problem - the coastal zone - a land of high-intensity urbanization localized where the sea and our citizens interact. Florida is blessed by a long coastline of beautiful beaches, indented by estuaries, lagoons and spring fed rivers. Rocky and sand covered islands invite habitation. A large and varied fauna and flora make recreation an avocation and work a pleasure. Accompanying these people are all the sustaining, and satellite industries that find the climate, labor, and commodity markets, cheap water transportation, and natural resources to be attractive. It is estimated that by the year 2008 a megalopolis will stretch down the Atlantic Seaboard from Georgia to encompass the Keys and extend along the Gulf to Alabama. This city will be fenced by the sea on one side and by the water management works, necessary to provide the water supply for this complex, on the other. What can we do about increasing the amount of water available for this population and decreasing the resultant wastes??? Rarely has there been tendered a more favorable opportunity for a coordinated planning and development project that will provide public access to beaches and multiple use of the coastal lands. Florida, as a peninsula swept by ocean breezes, having a largely indigenous water supply and only the beginning of the pollution of estuarine and coastal waters can cope with air, water and coastal dissipation and pollution, if we have a beginning at providing a constant water supply and at limiting pollution. This answer would appear to lie underground, where the porous limestones are interbedded with impervious fine-grained sediments and ground-water that circulates through these aquifers empty to the ocean and Gulf along the continental slopes.

Jan 1, 1969

By W. A. Haley

This paper discusses how a large wheel loader should be equipped, with particular attention paid to tires and tread life, and describes the several steps that can be taken to provide favorable working conditions and reduce over-all costs. A comparison is then made of wheel loader production and costs vs those of power shovels, and the present and possible future applications of the wheel loader are outlined.

Jan 1, 1969

By Richard R. Zupp, David A. Stevenson

A theoretical treatment of austenitic Fe-C-Z solutions (where Z represents a substitutional solute) was developed by extending a solution model which was previously applied to austenitic Fe-C alloys. The model assumes that each carbon atom in the solution excludes H interstitial sites from occupancy by other carbon atoms rmd thai otherwise the assembly of carbon atoms is equivalent to a modified Langmuir lattice gas. The results of the treatment provide theoretical justification for a phenomenological expression previously developed to represent the influence of substitutional solutes on the thernlodynamics of carbon in austenitic Fe-C-Z alloys. The expression is: where Kz is a parameter which characterizes the Fe-C-Z system at a given temperature and Xz and xj are the concentrations of substitutional solute and interstitial carbon expressed as atom ratios. The parameter, Kz, was associated with the differ- A number of investigators have measured the influence of various substitutional solutes on the carbon activity in austenitic Fe-C-Z alloys, where Z represents any substitutional solute. Experimental information is available for alloys containing the following substitutional solutes: Mn,&apos; Si,&apos; Ni,2-5 CO,&apos;-&apos;, Cr,5, 9-11 CU,4 Al,= v,11, 12 and Ti.13 This information is essential for studying many phenomena in Fe-C-Z alloys, particularly diffusion and diffusion-controlled phase transformations For example the pffprts nf various ence between the interaction energies between carbon atorns and host-lattice atoms in the Fe-C-Z solution and the corresponding energies for the Fe-C solution. The carbon activity in a ternary Fe-C-Z alloy, ac, was obtained in terms of the composition of the alloy and the single parameter, Kz: where y° is the Henry&apos;s law constant for the binary Fe-C solution. Both y° and H crm be determined from the data for Fe-C solutions, without recourse to any experimental data for Fe-C-Z solutions. The theoretical treatment was extended to alloys containing several substitutional solutes. By neglecting interactions between the substitutional solutes, an expression for the carbon activity in multicomponent alloys was obtained in terms of the Kz values characterizing ternary Fe-C-Z systems. substitutional solutes on the rate of pearlite growth is explained14 on the basis of their effects on carbon diffusion, which result from their influences on the carbon activity in the solid phases. In addition, recent studies have emphasized the dependence of the pro-eutectoid ferrite transformation15 and other diffusional processes in austenite16 on the influence of substitutional solutes on the carbon activity in austenite. They have indicated the need for suitable analytical expressions to represent such influences. The present authors previously developed general phenomenological expressions to represent the equilibrium partitioning of carbon between Fe-C alloys and Fe-C-Z alloys.&apos;2 The expressions are applicable to all the austenitic Fe-C-Z alloys for which experimental data are available, and are sufficiently simple to recommend their general application. For alloys in

Jan 1, 1969

By Paul Eimon

In the world of minerals exploration, computer-oriented data storage and retrieval methods are being talked about, studied and researched. The goal is to facilitate the recording, collating, indexing, recovery, and analysis of mineral deposit-prospect data. A survey has been made of the various report forms, suggested outlines, and computer coding forms that are currently used in mineral exploration to index and/or describe mineral deposits and prospects. These forms have a number of common characteristics: location, commodities, type of deposit, host rock, etc. Such basic mineral deposit-prospect "data units" are part of most exploration programs. "Data units" may be comprehensive bound published descriptions of mines or mining districts or 3x5 file cards or elaborate computer coding forms being developed in Canada. Initial attempts to develop computer-oriented information systems have run into the same roadblock: the lack of a body of organized, processible data describing the basic qualities of mineral deposits and prospects. To solve this problem, international committees are considering coding forms, world-wide semantics, and rules or standards for data collection and description. It appears that mistrust and lack of understanding of the computer; fear of loss of proprietary information; and disagreements over terminology are distorting the picture of what has to be done if the mining industry is to grow into more meaningful information systems for mineral exploration.

Jan 1, 1969

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of&apos; nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150&apos; C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-&apos;&apos; of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami&apos;s slution&apos; and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, &apos;Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,&apos;-* iron,&apos; and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By Ronald E. Feltman

Most engineering firms engaged in the design and manufacture of milling components and systems have established, through the years, a relatively well defined system design procedure. The process design engineer has at his disposal several alternative approaches to the successful completion of this task. Unfortunately, while these alternatives, at first glance, appear to be rather straight Forward, any attempt to implement them into a fully integrated commuter design program becomes increasingly more complex when one addresses himself to the problem in total. This paper summarizes Kennedy Van Saun&apos;s approach to the solution of this problem through a planned system design. Following the problem definition and discussion, a detailed analysis and system design synthesis is presented; the major aim here being to provide a system design which may be programmed and run on a relatively inexpensive computer installation such as the IBM 1130 system currently in use at Kennedy Van Saun. A summary section is also included, which Provides a general outline guide to the program systems design of equipment which, while quite different from milling system functionally, nevertheless lends itself to the approach used in this paper.

Jan 1, 1969

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

Four Mn-CLL alloys, containing 60, 70, 80, and 90 pct Mn, respectively, have been examined in the quenched and the quenched and aged conditions using electron microscopy and electron, neutron, and X-ray diffraction. After certain heat treatments the alloys transform from fee to fct and in the tetraom1 condition show a domain structure parallel to {101} planes. Neutron diffraction indicates that the domains are antiferrornagnetically ordered. The domain boundary contrast has been examined using bright- and dark-field microscopy, and the contrast effects observed under favorable conditions have been used to deduce the c axis orientation in each domain. The domains are extremely mobile and can be nucleated at precipitate particles and screw dislocations. The domain mobility is responsible for the high damping capacity. In the aged material a Mn precipitates in the Kurdjumov-Sachs orientation and results of both electron microscopy and neutron diffraction indicate that the matrix separates into two components—one rich in manganese and the other rich in copper. ALLOYS of manganese and copper have the unusual combination of a high damping capacity and good mechanical properties and have been the subject of a number of investigations as part of a general interest in high damping capacity alloys for engineering purposes.&apos;,&apos; SO far, however, there has been no reported electron metallographic study of these alloys. The Mn-Cu system has an extensive range of solid solubility at high temperatures, and the equilibrium phases are expected to be y (fee) and a Mn. The high damping capacity is associated with a metastable tetragonal structure of variable c/a ratio, which forms from the high-temperature y phase. This latter phase becomes more difficult to retain as the manganese content increases, and alloys containing more than 82 wt pct Mn undergo a reversible martensitic fcc — fct transformation on quenching. The X-ray work of Basinski and christian3 showed that the Ms temperature for the transformation was below room temperature for alloys in the range 70 to 82 pct Mn and increased linearly with manganese content. When quenched from the y region, alloys in the range 50 to 82 pct Mn are cubic at room temperature, but become tetragonal if aged at temperatures between 400" and 600°C. The martensite transformation occurs on cooling from the aging temperature. Tetragonal alloys have a banded microstructure and the bands analyze to be traces of (110) planes. Similar microstructures have been observed in In-Tl4 and in other manganese-base systems, such as Mn-Au5 and Mn-Ni.6 The mobility of the bands in Mn-Cu alloys can be demonstrated by optical examination of a polished specimen surface subjected to a cyclic stress.7 The bands appear and disappear as the stress is varied, and X-ray measurements of the (200,020) and (002) peak intensities confirm that a reversible reorientation of the tetragonal structure occurs. Meneghetti and sidhu8 investigated the magnetic structure of Mn-Cu alloys and found antiferromagnetic ordering in furnace-cooled alloys of composition >69 at. pct Mn. Magnetic super lattice reflections occurred at the (110) and (201) positions and the proposed structure was fct with the spins along the c axis. A more complete investigation by Bacon et al.9 confirmed this structure. The magnetic ordering temperature Tn was found to increase linearly with manganese content in the same way as the Ms temperature, and at any composition, Tn > Ms. This relationship suggested that the magnetic ordering was responsible for the cubic — tetragonal transformation in the manganese-rich alloys. The purpose of this investigation was to study the mechanism of high damping and the structural changes that occur on aging. The main technique used was transmission electron microscopy, but X-ray and neutron diffraction experiments were also carried out. EXPERIMENTAL Materials and Heat Treatment. The four alloys, provided by the Admiralty Materials Laboratory. were of nominai composition 60, 70, 80, and 90 Mn and all had low impurity levels, <0.05 pct C, <0.2 pct Fe. This material was cold-rolled to 200-µ strip with intermediate annealing and then given a final heat treatment of 24 hr in the range 800° to 900°C followed by water quenching. An identical heat treatment was given a length of 3/4-in.-diam bar of the 70/30 alloy from which the neutron diffraction specimens were machined. It was suspected that the tetragonal structures would be metastable at room temperature, and so the alloys were not aged until required for experiments. After aging in a salt bath the alloys were water-quenched. Thin Foil Preparation. Initial thinning to 50 to 75 µ was possible in a solution consisting of: 50 ml nitric acid 25 ml acetic acid 25 ml water The surface deposit and grain boundary etching was removed by a final electropolish at around 20 V in an electrolyte consisting of:

Jan 1, 1969

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.&apos; : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*&apos;" Exotic recovery processes have been considered primarily for &apos; perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969