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By J. David Lowell

On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radio- carbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy.

Jan 1, 1970

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

Jan 1, 1970

By Fathi Habashi

OXIDE ORES can be divided into two groups: 1) Simple oxides (Table 3.1). 2) Complex oxides. Those ores containing minerals composed of two oxides; an acid oxide (Cr2O3, Nb2O5, etc.), and a basic oxide (CaO, FeO, MnO), as shown in Table 3.2.

Jan 1, 1970

The C.S.A. copper-lead-zinc mine, located 7 miles north of Cobar in central-western New South Wales, is the largest known mineral ocurrence in the Cobar mining field. The generally discordant orebodies occur within a strike width of 600 ft and an overall strike length of 1200 ft. They are enclosed by the steeply westdipping, west-facing sediments of the Cobar Group, and comprise lenticular steeply north-pitching and eastdipping zones of sulphide mineralization which range in composition from massive pyrite-sphalerite-pyrrhotitegalena to less massive pyrite-pyrrhotite-chalcopyrite varieties.The thinly bedded siltstones, shales, and greywackes enclosing the mineralization appear to have derived some of their constituents from volcanic sources. They have been metamorphosed to the greenschist facies of regional metamorphism. At least two stages of deformation and folding have occurred. The first stage folded the rocks on a south pitching fold axis into their present configuration, and superimposed a strong axial plane cleavage which subsequently guided the emplacement of the mineralization. The second stage of deformation is considered to have controlled the zonal distribution of the orebodies.

Jan 1, 1970

By B. P. Bellport

This paper summarizes the Bureau of Reclamation's experience in the use of boring machines to excavate six major tunnels on the Bureau's water resources development projects in the western United States. The summary of experience is presented as a compilation of brief case studies for each of the six tunnels. Each compilation presents data on the tunnel dimensions, geological characteristics of the excavated rock, the tunneling machine used, machine operation, muck handling, method of tunnel support, ventilation system, and related information. The listing of the six tunnels in Table 1 reflects a diversity of tunnel lengths and diameters. However, despite this diversity of dimensions as well as the variety of rock encountered during excavation, the six tunnels have one major characteristic in common: their excavation was significantly expedited by the use of boring machines. Beginning with the 10,079-foot-long Tunnel No. 1 on the Navajo Indian Irrigation Project in New Mexico - the Bureau's first tunnel to be excavated by a boring machine - the boring machines, or "moles," have demonstrated their effectiveness in rapid and economical tunnel excavation. Tunnel No. 1, virtually 2 miles long, was bored through in 9 months, an unprecedented achievement in Bureau engineering experience, as compared with tunnels previously excavated by conventional means. Boring of the 45,630-foot-long Blanco Tunnel and the 26,610-foot-long Oso Tunnel, both on the San Juan-Chama Project in Colorado, set world records in rates of excavation,l/* Two days of exceptional progress highlighted the

Jan 1, 1970

By J. E. Terry

This paper outlines the steps that are being taken to close the gap between training and industry and indicates areas in which more work needs to be done. Although based on experience in the Maritime Provinces, it is applicable to industrial and educational studies across the length and breadth of Canada.

Jan 1, 1970

By Jack I. Paige

In this Bureau of Mines study, two fluidized-bed reactors were designed, built, and operated, one as a sorber for S02 and the other as a contactor for the regeneration of the sulfur-laden alkalized alumina. The target of 90 percent removal of S02 from a flue gas stream containing 0.3 percent S02 was attained by using a sorbent feed of 10-15 grams per minute into a 5-inch bed depth of alkalized alumina. The sorption unit was operated at about 330° C. Complete regeneration of the laden alkalized alumina containing 5 to 10 percent sulfur was accomplished in approximately 1/2 hour. An excess of reformed propane at about 730° C was the regenerating gas. Attrition losses, a major problem with this sorbent, ranged from 0.9 to 7.9 percent of the inventory. Data from these tests demonstrate, within experimental error, the validity of equations developed from short-term, thin-bed tests related to sorption and regeneration rates.

Jan 1, 1970

By G. E. Perry, R. D. Seba

The steam soak process is the most widely applied and most successful thermal supplemental recovery process in use today. This process, which consists of injection of steam in various quantities into a well that is subsequently used as a producer, can be repeatedly applied to the same well. The treatment, if successful, will increase the production rate of the well for a given period. For this reason, the steam soak process should be considered primarily as an acceleration method rather than as a method for producing oil that could not be recovered by primary means. However, application of this process to reservoirs containing viscous crude may produce oil that otherwise would have zero present value or would be produced at such low rates by primary methods that it would not be profitable. A major necessity for the successful application of the steam soak process is a source of natural energy. This source of energy may exist in one or more of the following forms: expansion of fluids, compaction, gravity drainage. This study was undertaken to determine the effect of gravity drainage on steam soak production and recovery and to develop a method for predicting production rates, ultimate recovery, and heat requirements when applying this process to a reservoir in which the primary driving mechanism is gravity drainage. (For additional discussion of some of the factors that affect recovery of viscous oils by the steam soak process, see Ref. 5.) Model The model developed for analyzing the performance of the steam soak process in gravity drainage reservoirs is a modified form of that developed by Matthews and Lefkovits.1,2 The model used in this study consists of two concentric cylindrical volumes of productive formation with cap and base rock of impermeable material. The inner cylinder, extending from the radius of the wellbore to some predetermined radius, is referred to as the hot zone; and the outer cylinder extending from the exterior boundary of the hot zone to the outer drainage boundary will be referred to as the partially heated zone. Fig. 1 is a schematic cross-section of the model, indicating its thermal properties. Horizontally the reservoir is divided into two regions, the upper region having a high gas saturation and residual liquid saturation, and the lower region containing a high liquid saturation. The boundary between these two regions is referred to as the free surface, which drops and changes shape as fluid is produced from the reservoir. The model was used to analyze the steam soak process by applying the following assumptions: 1. The horizontal formation is composed of one or more homogeneous noninterconnected layers containing incompressible fluids. Each layer is treated separately. 2. The hot zone is heated by the initial soak and is maintained at the steam temperature corresponding to atmospheric pressure by resoaking. 3. The height of the free surface at the producing well is at all times zero (producing well is pumped off). 4. The position of the free surface at the start of

Jan 1, 1970

By Frederick T. Fischer

The New Jersey Zinc Company began a program of exploration in Middle Tennessee in 1964. The target horizon of the exploration project has been the Knox Dolomite which is a low-yield aquifer over nearly the entire Central Basin of Tennessee (1). With the exception of a few hundred acres in the Wells Creek and Flynn Creek disturbances (astroblemes?), the Knox Dolomite in Middle Tennessee is known only in subsurface. In January of 1969, New Jersey Zinc announced the discovery of a major zinc deposit near Elmwood, southeast of Carthage. This is on the northeastern flank of the Nashville Dome where the nearly flat-lying beds have an average eastward slope of about 50 feet per mile. The anticipated development of a mining situation has emphasized the significance of hydrologic relationships in the region as a whole and especially in the Elmwood area. These relationships affect several areas of concern which ma be generally grouped into two broad classes; i. e. , (1) Problems of a Public Nature - involving the prevention of the contamination of potable aquifers, the prevention of the contamination of surface waters, the prevention of the capture of presently utilized water, etc.; and (2) Problems of Mining Economics - involving pumping capacity and costs, the possible need for equipment of special composition, underground environmental conditions, etc. Exploration drilling in Middle Tennessee has contributed additional information about the Knox aquifer and

Jan 1, 1970

The effect of conditioning energy input on the metallurgical results of an emulsion flotation process has beenattributed by previous authors to a detergency process.This paper shows that such a process does not explain the data and that an attrition mechanism is more appropriate.

Jan 1, 1970

SUMPEARY OF CURRENT PRACTICES History The outcrop and surrounding area of Comincots Sullivan Mine was originally mined by small open cuts on surface and small open stopes underground to which shafts and adits were driven for access. When it was established that a commercial grade of ore was available, an adit was driven on the 4600 level (feet above sea level), and OM was extracted by larger scale open stoping leaving supporting pillars where necessary. After the depth of the ore body was proven to the 3900 level and an adit driven at this level, many miles of drifts, crosscuts, raises and sublevels were driven for the extraction of the ore above this level. Larger open stopea were extended from this development. The mining method was, and to a very limited degree still is, a benching method. Due to the strong hanging wall in this area of the mine, stopes with a width of 100 feet or more were opened. In 1931, because the orebody was proven to extend below the 3900 level, a winze was sunk from the 3900 level to the 3350 level. From this winze three intermediate levels were opened. Following a plan of development well in advance of production requirements, further sinking was done by winzes and eventually a large shaft was raised to surface. Prior to 1958 the 2850 level was bottom which since that time has been extended to the 2500 level. Open stopes were developed and mined as this area was opened up.

Jan 1, 1970

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By E. D. Slone, F. L. Dillard

When a new mine is in the planning stages, one of the most important decisions to be made is the selection of' face haulage equipment and the interrelated transportation system to the surface. Equally important is the method of transporting personnel supplies and repair parts from the surface to the working places. When Bell & Zoller management elected to open the new Zeigler mine in the No. 9 seam near Madisonville, Ky., last year, various transportation systems were considered. It was agreed early that a slope mine would be preferred to a shaft mine, and that belt conveyors would be more economical than a rail system.

Jan 1, 1970

By P. N. Richards, M. K. Ormay

Commercially hot-rolled low-carbon steel strip may have one of two basic types of orientation texture, depending upon the amount of a iron which was present during the finishing passes. The changes in these textures with varying amounts of cold reduction up to 95 pct have been determined for the sheet surface plane and for parallel planes down to the mid-plane. The development of cold reduction textures has been reassessed on the basis of (200), (222). and (110) stereographic pole figures and pole density or inverse pole figure values. In agreement with the literature, it is shown that the textures can be described in terms of partial fiber textures but alternative descriptions are given for one of the fiber textures, in order to more closely correlate with experimental data. One partial fiber texture consists of orientations of the type (hkk)[011] extending from (100)[011] to {322}(011) in agreement with the literature. At moderate amounts of cold reduction, a second partial fiber texture forms with a <331> fiber axis inclined 20 deg to the sheet normal and a range of orientations centered on one close to (1 11)[112] and reaching to (232)[101] or (322)[011]. An alternative description involves a (111) fiber axis parallel to the sheet normal but capable of rotation about the rolling direction with rotation about the fiber axis. ORIENTATIONS developed in low-carbon steel strip after cold reduction are of commercial importance because they control, in part, the final preferred orientations after subsequent annealing. The method of control however is not understood completely. Some preliminary work indicated that the cold-reduced orientations and the subsequent annealing textures of commercial low-carbon steel were dependent on the orientations present in the material before cold reduction, that is, those present in the hot-rolled strip but, to date, the effects of initial orientations have not been extensively investigated. For this reason, much of the information given in the literature on development of preferred orientation is difficult to assess as details of initial texture and processing conditions are often inadequate or are altered by a subsequent heat treatment such as normalizing.&apos; It is known2 that anomalous results for near surface orientations may be obtained if lubrication during cold rolling is not adequate but whether lubricant was used during the experiments has not always been given, nor has the exact depth below the surface at which determinations have been made. A comprehensive review of cold rolling textures has been made recently by Dillamore and Roberts&apos; and more restricted recent reviews are due to stickels4 and Abe.5 Based largely on the experimental work of Bennewitz,1 reviewers have accepted that the preferred orientations produced on cold reducing low-carbon steel can be described in terms of two partial fiber textures as follows: Partial Fiber Texture A which has a (011) direction in the rolling direction and includes orientations within the spread from (211)[011] through (100)[Oll] to (211)[011.]; there is some controversy as to whether it extends as far as the orientation (111)[011]. As Dillamore6 has observed, the extent of this partial fiber texture depends on the intensity levels selected. Partial Fiber -texture B which has a (011) direction located 60 den from the rolling direction in the plane containing the rolling direction and the sheet normal. There are two directions which satisfy these conditions and orientations in this partial fiber texture extend from (21l)[0ll] through (554)[225] to (121)[101]. The orientations {211}(011) are members of both partial fiber textures A and B and it can be noted that a variant of {554)<225> is within 6 deg of a variant of {111}(112). Barrett7 had postulated earlier that, in addition to orientations which would fall into partial fiber texture A, a true fiber texture with a (111) direction in the sheet normal was present after heavy cold reduction. This fiber texture would include orientations such as {111}(011) and {111}(112). Later investigators, notably Bennewitz,&apos; have discounted this, mostly on the ground that the partial fiber textures A and B, as described above, contain all the strong orientations that have been observed. However in other work it has been reported2 that (222) pole density or inverse pole figure values show a continuing increase with increasing reduction by cold rolling and give values considerably greater than for any other low indices plane. Thus it could be inferred that a (111) fiber texture as described by Barrett would be one which becomes more dominant with increasing cold reduction, whereas Bennewitz&apos; concluded that components such as {554)(225) in partial fiber texture B began to decrease in intensity at high reductions. Following Bennewitz, one would expect a decreasing (222) pole density value (parallel to the sheet normal) with increasing cold reduction. Because fiber textures consist of grains with a range of orientations that have one axis in common, it has been inferred that during deformation the crystal orientations rotate about the fiber axis&apos;74 and that the orientations of crystals that at one stage belong to one fiber texture can rotate on further cold reduction into the other fiber texture through an orientation in which the two fiber textures intersect.&apos; For example,

Jan 1, 1970

By Daniel C. Boteler

Five lignites from the northern Great Plains province were carbonized at temperatures from 500° to 1,000° C in a bench-scale unit. A replicated Greco-Latin square experimental design was employed to allow testing of four independent variables at five levels. Independent variables investigated were temperature, source of lignite (mine), weight of charge, and moisture content of charge. Dependent variables were char yield, tar yield, light-oil yield, tar plus light-oil yield, carbonization gas yield, and carbonization gas heat yield. An analysis of variance indicated that, at the 99-percent confidence level, the independent variables of carbonization temperature, source of lignite, and weight of charge were significant for yields of char, tar plus light oil, and carbonization gas, whereas moisture content was only significant for carbonization gas yields. At the 95-percent confidence level, moisture content significantly influenced the carbonization gas heat yield per pound of lignite charge and the yields of dry tar plus light oil. All dependent variables were determined on a moisture- and ash-free basis. Multiple regression equations for predicting seven different factors of carbonization yields as functions of carbonization temperature and initial composition were developed using computer techniques. Equations for yields of char, tar plus light oil, and carbonization gas were compared with equations previously developed by others at the 500° C level.

Jan 1, 1970

By K. Robert Dorman

Spray-applied polyurethane foam was used to insulate the walls of heated rooms excavated in permafrost. The experiment was designed to determine whether polyurethane foam can be sprayed successfully on frozen ground under freezing conditions and to measure the effectiveness of the insulation in maintaining--at elevated temperatures for an extended period--a room excavated in frozen ground. Two manufacturers&apos; foams were investigated in the laboratory. Subsequently, one of the foams was employed to insulate two small rooms, one in frozen gravel and one in frozen silt, in an experimental tunnel belonging to the U.S. Army Cold Regions Research and Engineering Laboratory (USACRREL) near Fairbanks, Alaska. Following insulation, heat was introduced into the two rooms. Heat migration across the insulating barrier into the walls, in addition to wall closures, was monitored over an 8-month period. The results show that polyurethane foam can be successfully sprayed on frozen ground in below-freezing temperatures. Given this type of insulation, together with winter cold to supercool the surrounding ground, it should be possible to maintain a shaft or heated room in permafrost for several years.

Jan 1, 1970

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano&apos; (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By G. R. Belton, R. J. Fruehan

The Knudsen cell-mass spectrometer combimtion has been used to study the Fe-Al and Ag-Al liquid alloys. By application of the recently developed integration technique to the measured ion-current ratios, activities have been derived for the Fe-A1 system at 1600° C and for the Ag-Al system at 1340"C. The results are partially represented by the following equations: Internal consistency between the data on silver-rich and iron-rich alloys is demonstrated by application of the literature measurements on the distribution of aluminum between the nearly immiscible liquids iron and silver. The usual restrictions on the ratio of the mean free path of the escaping atoms to the orifice diameter of the Knudsen cell are shown not to be limiting in this technique. DESPITE the importance of a knowledge of the activity of aluminum in understanding deoxidation equilibria in molten steel, no direct studies have been made of activities in liquid Fe-A1 alloys at steel-making temperatures. Lower-temperature direct studies have, however, been carried out on aluminum-rich liquid alloys by Gross, Levi, Dewing, and Eilson&apos; at 1300°C and by Coskun and Elliott&apos; at 1315°C. Apart from phase diagram calculations by Pehlke, other determinations have been indirect and were made by measurement of the distribution of aluminum between iron and silver475 and combination of these data with extrapolated activities in the Ag-A1 system.~-% ecently, however, Woolley and Elliott have made a significant contribution by directly measuring heats of solution in the Fe-A1 system at 1600°C. The present authorslo have recently employed a Knudsen cell-mass spectrometer technique in a study of activities in iron-based liquid alloys. In this technique activities and heats of solution are determined from a series of measurements of the ratio of ion currents of the components; and since ion-current ratios are used, problems caused by changes in instrument sensitivity or cell geometry are overcome. Results obtained for the Fe-Ni system were found to be in excellent agreement with previous work, thus demonstrating the reliability of the method. The present paper describes a similar study of activities in the liquid Fe-A1 and Ag-A1 systems, this latter system being included in order that a meaningful comparison can be made with the above-mentioned indirect studies. INTEGRATION EQUATIONS A detailed derivation of the equations used to determine the thermodynamic properties from the measured ion current ratios has been given elsewhere;&apos;&apos; however it is useful to summarize them here. By the combination of the Gibbs-Duhem equation with the direct proportionality between ion-current ratios and partial pressure ratios, it was shown that for a binary system at constant temperature and pressure: where al is the activity of component 1 with pure substance as the standard state, N, is the atom fraction of component 2 in the solution, and I; and t&apos;2 are ion currents of given isotopes of the components. The activity coefficient is given by: this latter equation being more suitable for graphical integration. Combination of Eq. [l] with the Gibbs-Helmholtz equation gives an expression for the partial molar heat of mixing: EXPERIMENTAL A Bendix Time-of-Flight mass spectrometer model 12! fitted with a 107 ion source and a M-105-G-6 electron multiplier, was used to analyze the vapor effusing from the Knudsen cell. The arrangement of the Knudsen cell assembly was essentially that of the commercial instrument (Bendix model 1030) but with several modifications. Instead of heating with a single tungsten filament, a cylindrical tantalum-mesh heater was employed. Up to 1400°C simple resistance heating was used but above this temperature electron bombardment between the tantalum mesh and the tantalum cell susceptor was necessary. The temperature was measured by means of a Leeds and Northrup disappear ing-filament type optical pyrometer sighted on an essentially black-body hole in the side of the cell. Details of the temperature control, temperature measurement, and in situ calibration of the optical pyrometer can be found elsewhere.I0 In the investigation of the Fe-A1 system the Knudsen cells were constructed of thoria crucibles with fitted thoria lids (Zircoa). The cells employed in investigating the Ag-A1 alloys were made up of high-purity alumina crucibles (Morganite) with lids of recrystal-lized alumina (Lucalox). The cells were 0.370 in.

Jan 1, 1970

By John F. Abel

"The most conservative persons I ever met are college undergraduates." Woodrow Wilson said that in 1905. No one is saying anything like it today. Chaos on the campus was a cliche of the sixties. Since 1905, education has expanded in every direction. Many more people are being educated for much longer periods of time. The school-leaving age has risen from 14 years to 20 years, on an average. Many are in school until after their 25th birthday. On the surface this situation appears all to the good. Our technical society needs a massive yearly infusion of semitrained (or educated, if you prefer) new blood. The efficiency of our economy and our standard of living are tied to high individual productivity which can be achieved only with an educated work force. Our democratic institutions are said to be founded on an educated electorate.

Jan 1, 1970