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By Walter J. Karplus, Otto J. M. Smith

The transient response of earth formations may be tlcter.171ined by means of four electrodes mounted coli-rienrly on n sonde. Exponentially decaying current pules are applied to one pair of electrodes and the re.rrrlting voltage transient at the other pair is recorded. It is shown by theoreticol analysis and verified by laboratory experiments that this arrangement readily yields the direct resistivity of the formation and provides valrrable additional information as well. INTRODUCTION Although electrical transients have been employed with moderate success in geophysical prospecting, their application to well logging has received virtually no attention in technical literature. In the conventional direct resistivity logging methods only the zero frequency impedance of the formation under study is measured, and no information is obtained regarding its reactive characteristics. Since the use of certain transients appears to offer some advantages in this respect, experiments were performed on a laboratory scale to investigate this possibility. This investigation was limited to a study of a four-electrode array where both the receiving and transmitting electrode pairs are mounted on a logging sonde, and decaying exponential pulses are applied to the transmitting electrodes. THEORY Given an electrode configuration as shown in Fig. I, located in a homogenous medium of resistivity p, if each electrode has an effective radius, r, which is small compared to the spacing, s and a, it is easy to show by integrating the volume resistivity that the input resistance, Rrw, of the transmitting electrodes is Rxw=p/2pr If a capacitor of capacity C, charged to a voltage Em, is suddenly connected to these electrodes, the resulting current, I(t), will then be The voltage transient, E(t), at the receiving electrodes may then be found by substracting the resulting potential at electrode Y from that appearing at electrode Z. and by inserting Eqs. 1 and 2 Integrating Eq. 4 with respect to tim

Jan 1, 1957

W. G. MITCHELL,* New York, N. Y.-I quite agree with Mr. Wilson1 in the statement that the Bonanza copper orebodies of the Jerome District are definitely pre-Cambrian. You might go much further than that. It is an interesting fact and, I think, well substantiated that the chalcocite enrichment is pre-Cambrian, and in that particular the deposits are unique, so far as I know, among copper-ore deposits. It is certainly true, under my scheme of classification, at least, and I think it has been supported by the work of Mr. Reber of the United Verde Extension, that chalcocitization was entirely accomplished prior to the laying down of the Cambrian sediments. The statement of Mr. Wilson that no Yavapai schist, as defined by Jagger and Palache, has been found in the Jerome District and that the schist in Jerome is composed entirely of ancient intrusive and extrusive volcanic rocks and bedded tuffs is one with which I am not entirely in accord. I believe that it is true that the schists at Jerome are largely composed of bedded volcanic material, I am also certain that there is a considerable proportion of plastic material in those schists. I have seen a good many slides, and it is quite common to find quartzites and limestones in the schists. At a short distance from Jerome, at the Arizona Binghamton, there are limestone strata in the schists several feet in thickness, and unmistakably a part of the original sediments as laid down. Another statement of Mr. Wilson is supported by my own observations. In the United Verde mine included fragments of sulfide ore are found in later anthracite dikes, which cut the orebodies but do not invade the chalcocite sediments. This is not only true, but those fragments of sulfide ore that are of small size, from the size of a walnut to fragments 2 and 3 ft. in diameter, are of the original unenriched pyritic material. I have never found high-grade ore, either chalcopyrite or chalcocite, in any of those dikes.

Jan 4, 1919

By R. W. Raymond

At the Pittsburg meeting of the Institute, in March, 1910, the death of Mr. Metcalf was announced, and Col. H. P. Bope, of Pittsburg, delivered in memory of him a brief but eloquent address, which, though expressing the Norrow of Mr. Metcalf's friends, and, in general terms, the debt of gratitude which his country and his profession owed to him, was not intended to be a complete survey of his life and work. With Colonel Rope's permission, and with the aid of some of the statements in his address, I substitute for it, in our Transactions, this more cletailed, yet still inadequate memorial. As Colonel Rope justly remarked, the men who could do justice to this theme—such men as Jones, Chalfant, Bennett, Oliver, and Park—passed away before Metcalf, leaving him almost the last of the generation of great steel-makers who made Pittsburg the Sheffield of America, and who discharged a double function, as the rearguard of the old metallurgical practice and the ran-guard of the new. I knew many of them; would that I were better qualified to celebrate their achievements. William Metcalf was born Sept. 3, 1838, at Pittsburg, Pa., where his father, Orlando Metcalf, was an eminent member of the bar. At the age of sixteen, he entered the Rensselaer Polytechnic Institute, at Troy, N. Y., from which he was graduated in June, 1858: Returning to his native city, he became an assistant engineer in the Fort Pitt Foundry, of which he was made Superintendent in 1859. This famous establishment produced the largest castings and heaviest machinery then knolrn in the United States; and Mr. Metcalf's intense, intelligent and incessant study of his business prepared him as a manufacturer for a patriotic service to his country more valuable than, as a soldier, he could have rendered in the field. The call came in 1862, when the government needed, above all things, a supply of field, naval and siege artillery. The

Jan 1, 1911

By Lawrence Addicks

SOME three years ago the smelter connected with the Chrome, N. J., refinery of the United States Metals Refining Co. found itself embarrassed y constantly increasing piles of unsmelted blast-furnace flue dust. The charge was fine and 10 to 15 per cent. of it was blown over into the flue. Sulphur was at that time too scarce to make the sintering of the finer part of the charge attractive, and raw-ore smelting in a reverberatory with a partly oxidized charge. was not to be thought of. A great many schemes were considered, including leaching, blowing into the converters, and briquetting, the problem finally narrowing down to blast roasting and nodulizing. It was found by experiment that blast roasting would not yield a satisfactory sinter without the addition of coke dust or sulphide fines to augment the fuel value of the flue dust, and on this account, together with the low first cost of a kiln, the latter was decided upon. A couple of tons of flue dust Were tried out in the experimental kiln in the laboratory at Yorktown, Va., of J. H. Payne, who acted as consulting engineer in this connection. This kiln was approximately 2 ft. in diameter and 20 ft. long and Was fired with fuel oil. A run of several hours yielded excellent nodules. The kiln showed no tendency to build in and form "nose rings" and gave a fuel consumption of 50 gal. of oil per ton of flue dust. There was no indication of any stack loss. The roasting was strongly oxidizing. A study of what full-size kilns were doing on cement clinker and on nodulizing pyrites cinder indicated that a 60 by 6 ft. kiln would certainly not consume over half of the oil per. ton of flue dust shown on the test and as fuel oil at that time Was selling around 2 1/2 c. per gallon it was decided to let it go at that.

Jan 7, 1914

By H. M. Howe

One of the little electric-resistance magnesia crucible-furnaces which I designed for the metallurgical laboratory of the School of Mines of Columbia University is shown, in vertical section, of full natural size, in Fig. 1. The furnace itself consists of two semi-cylinders of magnesia, A A, with a cover of magnesia, B B, and a stopper, C, also of magnesia, which is perforated to admit the leads x, y, of a thermo-electric couple. The furnace is heated by the spiral of platinum wire, D D (entering and departing by the openings I and K), through which a current of any desired strength is passed, bringing it to incandescence, and to ally temperature, not above the melting-point of platinum, which may be desired. The crucible E, actually used in this furnace, is also of magnesia. I have heard of some unsuccessful attempts with furuaces of this general class, and have attributed these failures to the use of siliceous materials for the furnace-walls. Of course such a result is what we should expect, since the silica mould readily be electrolysed by the current, and the resultant silicon would alloy with platinum ; but the little magnesia furnace here clescribed seems to be wholly free from this objection. It has been used in my laboratory for some months, and temperatures, up to 1100° C, hare been developed in it over considerable periods of time—indeed, it has been held near 1400" C. for about two hours—without indication, thus far, of any deterioration of the platinum. In the section shown, F F are a pair of steel disks, bound together, but separated by the inverted thermo-junction, N, of the thermo-electric pyrometer. This arrangement permits the observation and record of retardations in the heating and cooling of F F—in other words, the determinations of the cooling curves of steel—a purpose for which the furnace has been used, thus far, more frequently than in the determination of meltingpoints. For the latter operation, however, it is also suitable.

Jan 1, 1902

E. W. King, Bozeman, Mont.: The form of measuring up ore in sight looks very plausible, as illustrated in the paper of Mr. Emmons, but from my experience of many years of mining in Montana and Nevada, I have found it is very hard to measure up anything nearer than a guess of what you have in sight, except in the case of a true vein, or a flat vein where the boundaries are well defined. I have been interested in several miues with Dr. A. R. Ledoux, and I know that my foreman and myself, going into the mines and using our best judgment, could seldom see more than 30 days' supply actually in sight, and yet we were running from 100 to 250 tons a day, and keeping it up year after year. Prof. John D. Irving, New Haven, Conn.: I understand from Mr. Emmons that this is a method which has been found applicable in the copper-mines in Tennessee, where the record could be made with a good deal of accuracy, and where the work in the mines allowed the necessary development to be done, so that the record could be kept up. I do not think there was any intention in his mind to imply that this was applicable to all cases, especially such as Mr. King has mentioned. President Charles Kirchhoff, New York, N. Y. : I think the point is that the paper impresses the necessity for doing it where the possibilities exist. There has been too little attention given to this very matter, particularly in the United States; but I think our English friends are following it very much more zealously, and the demand for it there is possibly greater than it is here, because English boards of directors handle mines that are often very much further away than our own are, and the English public and the English engineers generally are very much more insistent upon seeing how much longer current dividends are going to last, or current assessments are going to continue.

Jan 1, 1913

A. V. ADAMSON,* New York, N. Y. (written discussion).-The experience of users of pulverized fuel in metallurgical work, particularly for open-hearth furnaces, has demonstrated that high ash and sulfur in pulverized fuel are a detriment, the sulfur in the coal entering into the finished product; hence, in this class of work it is extremely important, when pulverized coal is to be used, that the coal be selected with care, and only those having low percentages of sulfur be used, in combination with proper means for combustion. I have found that no general statement can be made as to the cost of pulverized coal, each installation being an individual engineering problem and necessitating a varying capital expenditure; as each installation has its own power cost, the actual cost of pulverizing varies between wide margins. It has been found that no general rule can he laid down as to either fineness or dryness; for some uses a wide range is permissible in both factors, while some classes of fuel require different treatment from others. Anthracite, coke breeze, and lignite ash will, under certain conditions, form slag, the melting point of the ash from fuel of this character being practically the same as of that from bituminous coal; furnace temperatures above the melting point of ash must therefore cause the formation of slag. However, it should he noted that furnace temperatures attainable with this class of fuel are not usually so high as those from bituminous coal, which probably explains the statement that the former do not slag. In a well designed furnace, temperatures above 2250° F. (1235° C.) will be obtained with that class of fuel, and slags will be formed. Too much attention apparently has been centered on high CO2 contents of stack gases. A high percentage of C02 is frequently obtained at the expense of the brickwork, the furnace temperature being increased by diminishing the excess air; a high percentage of C02 thus simply means a small proportion of 02.

Jan 12, 1918

By M. E. Nicholson

The solid solubility of boron in iron has been determined by saturating iron with respect to FeyB at several temperatures from 870° to 1135 C. In alpha iron the maximum solubility was found to be 0.002 pct B and in gamma iron the solubility varied from 0.001 pct at 915°C to 0.020 pct B at 1165OC. The eutectic and peritectoid temperatures were found to be 1165° and 911 °C respectively and the gamma iron solidus was located approximately at 0.020 pct B. RECENT investigations of boron-treated steels', ' indicate that the solubility of boron in austenite is of the order of 0.003 pct at 900°C. This has led to the general belief that the solubility of boron in a and r iron is considerably less than that indicated by Wever and Muller." Therefore the solid solubilities of boron in a and r iron have been re-determined. The eutectic and peritectoid temperatures were also remeasured and the r-iron solidus was studied in some detail.* In 1929 Wever and Miiller investigated the phase equilibria of Fe-B alloys. Fig. 1 shows the solid solubility region of the Fe-B diagram based on their investigation. They found that boron lowered the A, transformation temperature to 1381 °C where saturated 6 solid solution "which must contain about 0.15 pct B" and "r solid solution containing about 0.10 pct B" are in equilibrium with liquid containing 1.9 pct B. At the eutectic temperature of 1174"C, 7 solid solution was found to contain "about 0.15 pct B." A peritectoid relation was found to exist between a and y iron with an invariant temperature at 915 "C, where the boron solubility in 7 iron was "about 0.10 pct B" and the solid solubility in a iron "did not exceed 0.15 pct B." Although most of their

Jan 1, 1955

By D. I. Bardos

The occurrence of Laves phases (AB,) in various binary alloy systems has been reviewed in recent papers.13 Iron forms Laves phases with Sc-, Ti-, V- and Cr-group elements. However, two of the corresponding Laves phases with cobalt, namely MoCo, and WCo,, are missing. Nickel forms binary Laves phases with Sc and Y, but not with any Ti-, V-, or Cr-group element. These conditions are schematically illustrated in Table I. That electron concentration is a significant factor in determining which type of Laves phase is formed in a given case was recognized long ago by Laves and Witte,4 This concept has been more recently applied to Laves phases formed by transition ele-ments. It now appears that the average electron concentration (average number of electrons per atom outside of the closed shells of the component atoms) may be an important factor also in determining whether or not a Laves phase can occur at all in a given system. As shown in Table I, in the transition element systems considered Laves phases are absent at electron concentrations of 8, or larger (to the right and below the double line in Table I). These absences clearly cannot be accounted for on atomic size considerations, as evidenced by the many inconsistencies apparent in Table 11. While the ideal radius ratio for Laves phases is 1.222, in the systems which do have Laves phases the ratios of CN 12 radii range from 1.10 to 1.46. The consistent absence of Laves phases at RA/RB< 1.10 might be attributed to the low values of these radius ratios. However, Table II shows that absences also occur irregularly throughout the radius ratio range covered. In a previous paper7 it was concluded that, in transition element systems forming u-phases, silicon may act as an acceptor of electrons, thus stabilizing the u-phase at electron concentrations higher than

Jan 1, 1962

By Robert H. Richards

OF the several professions-the chemist, the civil engineer, the mining engineer, the mechanical engineer-the courses of instruction, as arranged at the scientific schools, differ considerably as to the amount of practical information which the student is able to gain. The analytical chemist has facility for a very thorough review of the processes which he will be called upon to perform. The student in civil engineering by his field practice learns the use of his tools and the art of taking field-notes. The mechanical engineering student is in the vicinity of machine-shops, which he can visit, and at which he can work. The student in mining engineering has no such advantages. The mines are at a distance, and the railroad fare to get to them is oftentimes an insuperable difficulty. The aim of these laboratories is essentially to give to the student in mining and metallurgy a chance to study on a small scale the practical parts of his profession. We cannot, in a small laboratory, build a mine to timber, to work, and to survey; we cannot make artificial quicksands and other impediments to mining. In short, we cannot study exploration; but we can study the mechanical preparation and the subsequent smelting of ores. Before presenting the plan of these laboratories it may be interesting to indicate the progress of the idea from its beginning. During the summer of 1870 President Runkle visited the mines of Colorado, and while there, conceived the idea of making an expedition with the mining students to some of the Western mining regions. He talked over the scheme with many railroad and mining men, and everywhere received encouragement. In the summer of 1871 the Institute party visited the mines of Colorado, and spent six weeks in taking notes of them. President Runkle here conceived the idea of building up a mining and metallurgical laboratory ; and by the aid of Booth & Co. of San Francisco, a stamp-mill was obtained, with the Washoe silver-working apparatus. During the year

Jan 1, 1873

By H. R. Froning, R. O. Leach

In wertability alteration flooding, a chemical agent is rnoved through a reservoir by the flood water to increase oil recovery by decreasing the degree of wetting of the rock by the oil. Substantial amounts of the chemical may be lost during movement through the reservoir. The extent of the loss, and therefore the economics of the process, depends in some cases on factors which are difficult to reproduce in the laboratory. Therefore, a short-duration, low-cost field test method is needed to permit evaluation of chemical requirements under actual field conditions. This paper describes a small scale rest conducted at a single well for measuring chemical requirements, thereby giving a more reliable evaluation of this important factor in the applicability and economics of the process. In the rest a small wafer slug containing the chemical agent and a nonadsorbed tracer is displaced into the reservoir by a known volume of wafer. The well is then placed on producrion. Chemical loss per barrel of pore volume contacted is calculated from [he fractional recoveries of the agent tested and the nonadsorbed tracer. The method has been used to determine within the actual reservoirs the chemical requirements for both a sandstone and a dolomite reservoir. Several chemical agents are potentially available for wettability alteration flooding, although none is universally applicable. For some applications of the method, chemical costs per barrel of additional oil recovered can be substantially less than one dollar. INTRODUCTION Wettability alteration flooding provides a means of increasing oil recovery from reservoirs by decreasing the degree of wetting of the rock by the oil and increasing the displacement efficiency of the flood water. Earlier studies demonstrated a relationship between oil recovery during waterflooding and the degree of wetting of a rock surface by an oil. The application of wettability alteration flooding to the Harrisburg field of Nebraska provided a field test&apos; of this recovery process. Subsequently, additional laboratory and field tests have developed additional procedures for evaluating wettability alteration flooding, and have indicated where the process may be applicable. Applicability of this process to specific reservoirs is determined by a progression of tests to determine sus- ceptibility of the reservoir to alteration of its wettability, to indicate the degree of recovery improvement and to estimate the amount of chemical required to process the reservoir. The economics of applying improved oil recovery processes depends not only upon the degree of improvement in oil recovery achievable by the process but also upon the process costs and the timing of the income and the investment. Emphasis in this paper is on the expenditure aspects of the process. The work reported in this paper indicates that the chemical investments required for wettability alteration flooding are substantial. For evaluating the economics of a potential flooding application it is imperative that a sound estimate of the chemical requirements be made for the reservoir. Generally, true reservoir conditions are not adequately simulated in laboratory chemical propagation tests. Because of wide well spacings, many years might be required to obtain chemical propagation data from conventional pilots or inter-well tests. Consequently, n short-duration, low-cost method is needed to determine chemical requirements in the field. The potential applicability of wettability alteration flooding is discussed, as well as the economics of wettability alteration with respect to the inherent and imposed restrictions on the timing of income and investments. DETERMINATION OF CHEMICAL REQUIREMENTS In the process of moving a chemical bank through reservoir rock, some of the chemical agent lags too far behind the flood front to be effective or is otherwise lost to the reservoir system. The extent to which these losses occur overshadows the reductions in chemical concentration due to diffusion and to mixing with the reservoir fluids. Experience indicates that almost without exception, chemicals which induce a wetting change undergo either sorption reactions or chemical reactions with mineral constituents of the pore surfaces. Other reactions may occur between the added chemical and the reservoir oil and water. Even in limiting consideration to reactions of the relatively inexpensive inorganic salts, bases and acids, the reactions may be exceedingly complex. Reservoir pore surfaces consist of more than silica in sandstone reservoirs, and more than calcite or dolomite in carbonate reservoirs. Many mineral species are present, each exhibiting specific tendencies to react with an injected chemical. The reactions which occur can consume enough of the agent to have an important effect on economics. These reactions can cause a change in pH of the chemical bank, or may remove some of the active chemical by precipitation, adsorption or reaction to form a new chemical which may or may not be effective in

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

The tensile properties, creep resistance. and thermal stability of highly alloyed Ti-Al-Zr alloys were examined. On the basis of these studies, the Ti-7Al-1ZZr composition was selected for more complete evaluation. The alloy was found to be weldable and free from excessive directionality. In addition, it developed maximum properties without requiring heat treatment other than an annealing operation in the alpha field. The alloy was recommended for scale up and is presently being investigated on a production-level basis. One of the more attractive properties of titanium alloys is their ability to withstand stress at moderately high temperatures, and a considerable amount of effort has been devoted to increasing the maximum service temperature of titanium alloys. This work has suggested that the optimum alloys for high-temperature service will be single-phase a (close-packed hexagonal) alloys containing significant amounts of aluminum. However, the maximum amount of aluminum which can be alloyed with titanium is between 6 and 8 pct,l since at high-aluminum contents an embrittlement reaction occurs in the anticipated service temperature range, 800" to 1100°F. It has been shown that the embrittlement reaction involves decomposition of the high-aluminum a phase to one or more new phases.&apos; Since this reaction does not occur at intermediate or low-aluminum contents, it was felt that intermediate Ti-A1 alloys might be strengthened by a-soluble ternary additions without inducing the embrittlement reaction. The first alloying addition considered was tin, which shows extensive solubility in a titanium and has moderate strengthening tendencies. Unfortunately, it was soon apparent that tin also promoted the embrittlement reaction, and that to obtain a stable alloy, the aluminum content had to be reduced as the tin content was increased. The second alloying addition considered was zirconium, which is similar to tin in its effects on titanium. This element did not contribute to the embrittlement reaction and, in fact, appeared to increase the maximum amount of aluminum which could be alloyed with titanium without inducing instability. This paper describes an investigation of the Ti-A1-Zr a alloy region. Alloys containing from 4 to 12 pct A1 and from 6 to 15 pct Zr were examined. The properties of these alloys are described and the bases for selecting an optimum composition is outlined. This composition, Ti-7A1-12Zr, is presently being scaled up in tonnage quantities, and is being evaluated extensively throughout the industry. In addition to presenting the basis for its selection, this paper presents a description of the properties developed in laboratory material as determined during the alloy investigation. These properties suggest that this alloy can fill an important position in applications requiring light weight, fabrica-bility, weldability, and strength to 1000oF or higher. EXPERIMENTAL PROCEDURES Titanium alloy ingots were prepared by inert electrode arc melting under an argon atmosphere. Alloying elements used were 110 Bhn titanium sponge, high-purity aluminum, and reactor-grade zirconium. Pancake-shaped ingots were prepared weighing approximately 300 g. The composition of the ingots was checked by weight measurements before and after melting. The pancake ingots were forged at 2000°F to approximately half their original thickness to give a flat plate roughly 1/2 in. thick. This plate was then rolled at 1800&apos; to 1600°F to 0.250 in. thick. All of the alloys examined fabricated well. However, alloys containing 15 pct Zr tended to overheat due to exothermic oxidation, and scaling was excessive. As might be anticipated from its effect in decreasing the ß transus, increased zirconium appeared to improve fabricability somewhat, especially during rolling at lower temperatures. Except for a limited study of heat-treatment response, all alloys were examined in the a-annealed condition. Prior to heat treatment the a and ß tran-sus temperatures were determined by metallo-graphic examination of samples quenched after annealing at 50-deg intervals in the transformation region. These data are shown in Fig. 1. Recrystal-lization appeared to occur in about 1 hr in the range 1300º to 1500ºF. Therefore, alloys were annealed for 1 hr at 1550ºF (4 and 5 pct Al), 1600ºF (6 through 7-1/2 pct Al), or 1650°F (8 or more pct Al). This produced an equiaxed a grain structure. In most alloys, a "ghost" structure was visible after the a-annealing treatment, as shown in Fig. 2. This structure apparently resulted from the acicular

Jan 1, 1963

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10&apos; greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.&apos; In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By Lo-Ching Chang, J. Chipman

The perennial and increasing interest in the chemical behavior of steelmaking slags has led to numerous attempts to formulate the thermodynamic properties of these solutions. The classical view is that of a solution of the component oxides in which certain acidic oxides are more or less completely held in combination with basic or metallic oxides, the nature of the interoxide compounds being derivable from the chemical behavior of the slag or from the mineralogy of a solidified specimen. The known electrical conductivity of slags has pointed to the existence of ions in the solution and a number of attempts have been made to account for the observed facts of slag behavior on the basis of a theory of complete ionization of the solution. It is the purpose of this paper to examine, in the light of ionic theory, a number of recently published series of data on slag-metal and slag-gas equilibria, with the purpose of obtaining a more complete or more satisfactory generalization than has been possible on either of the single bases of simple compound formation or complete ionization. The attempt to formulate the ionic constitution of a complex solution is fraught with many uncertainties. An ion is not something that can be plucked from the solution and examined in detail, nor can its true formula be determined with certainty by any single experimental method. In attempting to express the composition of a slag by various ionic formulas it can be expected that alternative hypotheses of essentially equal merit will present themselves. In the present state of early development of the ionic theory of slags, it may be necessary to make some rather arbitrary choices of ionic formulas in the absence of su- cient information to yield complete certainty. Acids and Bases The classification of slag-forming oxides as acidic or basic apparently dates back into the days of Berzelius. It is difficult to see how the concept could have originated in the early twentieth century when it was fashionable to define an acid or a base as an aqueous solution containing hydrogen or hy-droxyl ions. It is, however, entirely consistent with the modern and more general theory of acids and bases. In this theory, as originally formulated by G. N. Lewis,&apos; a basic molecule is one that has an electron pair which may enter the valence shell of another atom thus binding the two together by the electron-pair bond. An acid molecule is one which is capable of receiving such an electron pair into the shell of one of its atoms. The acid, the base, and the product of neutralization may be either ions or neutral molecules. The product of such a reaction may itself be a base or an acid if it is further capable of giving or accepting an electron pair. Thus a base is a donor of electrons, an acid, an acceptor. In oxide slags the typical and ever-present base is oxide ion, 0-—. In behavior and in importance it is analogous to hydroxyl ion, OH-, which is the typical base of aqueous solutions. There is nothing in the chemistry of slags which is quite analogous to the acid H30+ in aqueous solutions. This is not surprising for in slag systems there is nothing which can be designated as a solvent and no ubiquitous positive ion. The chemistry of slags is in fact more complex than the chemistry of aqueous solutions and the concepts which must be evoked in its study are correspondingly broader. In seeking a basis for a classification of slag-forming oxides as basic or acidic it must be remembered that these terms are not absolute but relative. A substance which acts as a base toward a second substance may act as an acid toward a third. This is less likely to happen among strong bases or acids than among the weak ones; there are numerous examples of weak acids which under the influence of a stronger acid behave as weak bases. Such substances are called amphoteric. A classification of the glass-forming oxides has been proposed by Sun and Silverman² and further developed by Sun3 in which the oxides are arranged in order of decreasing acidity or increasing basicity, each substance being potentially capable of acting as an acid toward substances below it in the list and as a base toward those above it. It is based upon the relative strengths of the metal-to-oxygen bond as determined by the energy required to dissociate the oxide into its component atoms.&apos; Data are available for computation of this energy, at least approximately, for the oxides of slags and glasses. In general those oxides from which it is most difficult to remove the positive atom are the strong acids while those in which it is most loosely held are the strong bases. It is in the latter, of course, that formation of oxide ion occurs most readily as, for example, in CaO which in solution ionizes to form the weak acid Ca++ and the strong base O—. The order of arrangement found by Sun is shown in the first column of Table 1, to which have been added the data for

Jan 1, 1950

Jan 1, 1910

By John W. Rushton

This month&apos;s article concludes the series with maintenance design considerations in secondary crushing, grinding, and flotation circuits.

Jan 4, 1978

Jan 1, 1944

New Products Equipment

Jan 6, 1950

By Harrison R. Cooper

Safety considerations apply from two perspectives in conducting shaft inspections for production and service hoists. The first is to conduct the task more effectively while minimizing the possibility that shaft deterioration may go undetected. The second is to increase security and efficiency of the inspection team in fulfilling its duties.

Jan 11, 1979

Jan 1, 1944