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By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By H. W. Krotzer

ADOPTION on a commercial scale of electrolytic deposition of metals brought with it the problem of providing an acid-proof cell or tank. Where the electrolyte contained only a dilute solution of sul-furic acid, wooden, tanks with lead linings were gen-erally adopted. There were cases, however, where a lead lining was impractical as a result of the presence of nitric acid in the electrolyte or because of the method of handling the current for deposition. purposes. Wherever lead was unsuitable for this work, asphaltic mastic was used in its place. This material, in addi-tion to possessing acid-proof qualities and being an insulator for electrical current, is also cheaper than lead. The only reason that prevented the common adoption of mastic for all work of this type was that it was still an unknown, unproved. material; while lead, although more costly, could be relied on. There are several electrolytic tank-houses equipped with acid-proof mastic linings now in operation. The first large one was the series tank-house of the Balti-more Copper Co., where the mastic used was composed of natural asphalts and a silica aggregate. These lin¬ings are now seventeen years old and still in service. The next large plant was that of the Chile Exploration Co., at Chuquicamata, Chile, ,and it is with this that this article deals. Another plant of more recent date is that of the Nichols. Copper Co., Laurel Hill, L. I., and specifications for the new electrolytic tank-house of the Union Miniere du Haut Katanga call for mastic lining. It is also being tried out on a smaller scale or for experimental purposes by many of the larger metal-lurgical companies. Thus while mastic linings were adopted originally to meet operating conditions that prohibited the use of lead, they are now in a position to compete successfully with the standard lead linings that are in general use. The Chile Exploration Co. plant, with a total area of over a million square feet, giving satisfactory ser-vice under the most adverse climatic and metallurgical conditions can be truly called the pioneer in this work. ,This article will deal with the development of the acid-proof mastic linings in Chuquicamata from the original experiments begun in 1912 up to and including the final successful installation that has now been in service for a number of years.

Jan 4, 1927

Pennsylvania has been a leader in the pageant of industrial America because of her natural mineral re- sources, geographical location, and the ingenuity and industry of her citizens. Brick and other clay products were manufactured in Philadelphia in William Penn's time. Ores of iron, zinc, lead, and copper were mined and smelted in eastern Pennsylvania long before the Revolution. Coal was mined on a commercial basis in the anthracite region as early as 1820 and in the bituminous fields in 1830. The first canals and railroads were constructed to transport minerals and mineral products. Oil was struck at Titusville in 1859. A significant event occurred in 1855-the establishment of the Farmers' High School-Pennsylvania's first attempt to provide higher education for its youth. The Farmers' High School included instruction in geology, mineralogy, and assaying. In 1859 the laws of Pennsylvania transferred to the School the state geological and mineralogical collections formerly located in Harrisburg. Well-informed people are familiar with the effects of the Land-Grant Act of 1862. With inspiring words it established state institutions of higher learning where "the leading object shall be, without excluding other scientific and classical studies . . . to teach such branches of learning as are related to agriculture and the mechanic arts . . . in order to promote the liberal and practical education of the industrial classes in the sev-

Jan 1, 1950

By Fred McConnell

FROM beginning to end, the processes of coal stripping are of great interest. From the time the prospector enters upon the property to examine it and to prove it, until the coal is loaded into railroad cars, every step must be taken with careful thought and planning. In proving the merits of a prospective property, an examination and computation of the overburden is of almost equal importance to the determination of the extent and quality of the coal bed itself. Is the overburden hard, and will it require drilling and shooting? How many yards of it will have to be handled to produce a ton of coal? Will it remain in place when .put in the spoil bank, or will it spread and run back into the pit? Are the drainage problems serious, and what will it cost to handle the water? Does the coal have bad dips, and what will be the grades and curvatures for haulage? These are a few of the physical problems that confront the prospector, and they can be ascertained only by adequate and careful drilling and engineering of the property to be considered. The engineer is an ever-present necessity, not only in the prospecting but in the daily operation of the property after it has' been approved and developed. The first step in operation after the location of the tipple is the contouring of the surface to be stripped and the laying out of the pits for operation, having in view again adequate room for spoil, drainage, haulage and other problems. If the overburden is hard, as much of it is in the larger stripping areas, it must be drilled for shooting with churn or well drills, the holes continuing from the surface down to or near the coal bed. The location of these holes should be made, and marked with stakes, by the engineer, acting in conjunction with the shooting foreman. The usual practice is to drill holes 6 in. in diameter, although the present tendency is to increase the diameter of these holes so that they will hold, without springing, a larger charge of explosive. With the use of the old method of shooting, the holes were sprung or chambered several times with charges of dynamite, and in the cavity thus made, the explosive was placed, largely at the bottom of the hole; but with the use of liquid oxygen as an explosive, and with the later

Jan 1, 1931

By Alexander Field

The hot-rolling properties of a series of high-sulfur steels are described. From a consideration of the sulfur, manganese, and zirconium contents of these steels, it is shown that zirconium reacts with the sulfur content of molten steel in accordance with the equation Zr + 2S = ZrS2. Zirconium disulfide appears in the finished state as gray-colored inclusions, similar to manganese sulfide in plastic behavior and general appearance. Zirconium completes its act of deoxidation before proceeding to combine with sulfur and indirectly increases the effective sulfur-combining power of any manganese which may be present. IN A previous paper,1 the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of "red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the reaction between zirconium and sulfur in molten steel may he represented by the simple equation, Zr + 2S = ZrS2, and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion.

Jan 2, 1924

By Holt, Grover J.

PRIOR to :1937 any discussion of mining and transportation in the iron mines of Minnesota would have been limited largely to conventional methods which have been used for years in the iron ore industry. Today, however, an inspection trip to the crest of almost any open pit on the ranges will re- veal great progress underground mining and the transportation of underground ore have also developed rapidly and if and when underground mining of iron ore again becomes generally economically feasible; these mining methods will probably witness a transformation equal to that which has taken place in the open pits.

Jan 1, 1941

By Arthur T. Ward

DESPITE the intense preoccupation of most of those members connected with the mining, concentration, and reduction of iron ores, the luncheon and subsequent technical session of the Eastern Magnetite Committee were exceedingly well attended. Many of the older faces were absent, but new ones took their places. More than sixty, all told, took in the technical session. Chairman Crockett opened the session by calling upon Meredith E. Johnson, whose paper, with its accompanying graph, was in reality a comprehensive historical review of iron mining from colonial days to the end of 1941. with some notes on current expansion which indicates that New Jersey is destined to become a still more important. factor in the production of magnetite ores.

Jan 1, 1942

By John V. Beall

The forecast of continued growing demand for phosphate, chiefly for fertilizer, has caused a world-wide rush for deposits by a variety of companies many of which have never before mined phosphate rock. The newcomers are diversifying into this growth industry on the strength of certain capabilities. Among these are the availability of investment capital, mining or processing know-how and marketing experience. Product tie-ins have motivated some into the search. Companies with excess sulfuric acid or potential for making it are in this category. This acid is the most commonly used for dissolving phosphate rock to make phosphoric acid. Base metal smelting companies are prime candidates in this field with by-product acid from roasting processes. Producers of "sweet" natural gas, such as those in Louisiana and Texas, have a potential for recovering low cost hydrogen from excess gas production for the manufacture of ammonia, the main source of nitrogen for fertilizer. "Sour" gas producers, such as those in the Canadian fields, are making sulfuric acid that is combined with western U.S. phosphate to make fertilizer materials. The presence of one or two steel companies in the look-see for phosphate deposits is based on by-product ammonia from coke-oven gas.

Jan 10, 1966

By Howard N. Eavenson

The mines of the United States Coal & Coke Co. are located in the Pocahontas coal field, in McDowell County, West Virginia. Twelve plants have been opened and equipped, of which, by reason of the present business depression, only nine are now in operation. These twelve plants serve eighteen mines; some of the plants having several openings, in either the same seam or in different seams, tributary to the same tipple. Only nine of these mines are now being worked at the plants in operation. Construction work was begun in 1902, and coal from the first three plants started was shipped in December of that year. An additional plant was opened in 1903, two in 1904, two in 1905, two in 1907 and the last two in 1908. On Jan. 1, 1915, the plants have been in operation an average period of 8.8 years. The rules of the company, which have been in operation since work was first begun, are similar to those in use by the H. C. Frick Coke Co. at its mines in Pennsylvania, in which " Safety First" was incorporated as early as 1907; and it has always been the policy of both companies to look carefully after the safety of their employees. Although the field is an extension of the old Pocahontas field, the mines, located upon a new branch railroad, are away by themselves, and, as is usual in such cases, the class of labor attracted at first was temporary in character. The rapid development of the mines required the employment of many new men and officials each year; and, while the accident record from 1904 to 1909 was as good as the average of the field, it was felt to be not as good as it could be made, and a determined campaign was inaugurated for preventing accidents of all kinds. Fig. 1 shows the tonnage of coal produced per fatality, both total and for inside accidents only, at our mines; the tonnage per fatality of all West Virginia mines, and of those in the Pocahontas field. The purpose of this paper is not one of congratulation on the results so far accomplished, since the operating officials are not at all satisfied that the maximum is in sight, to say nothing of its having been reached; but to describe the organization and methods that have produced these

Jan 1, 1915

By AIME AIME

WHETHER by the Mohawk Trail, Sound steamer, air plane, railroad or any other route or mode of locomotion, all roads will lead to Boston the week of National Metal Congress, Sept. 21-25. The Institute of Metals and Iron and Steel divisions of the Institute are then to meet jointly at the Hotel Statler, and the American Society for Steel Treating, the American Welding Society, the Society of Automotive Engineers and the Iron and Steel Division of the American Society of Mechanical Engineers present carefully planned programs at their respective sessions. The National Metal Exposition will be held on Commonwealth Pier.

Jan 1, 1931

By Charles White Merrill, James W. Pennington

No metallurgical process developed in the 20th century compares with froth flotation in its effect on the mineral industry. Processes like gravity - concentration, amalgamation, and pyrometallurgical reduction are of ancient origin; others like cyanidation and electrolytic reduction were well established by 1900. Such metallurgical processes as heavy-media separation, ion-exchange, and solvent extraction belong to this century, but their influence is small compared with froth flotation. Data collected by the U. S. Bureau of Mines* in a canvass of 202 froth flotation plants reveal that, in 1960, 198- million tons of material was treated to recover 20-million tons of concentrates which contained approximately $1 billion in recoverable products. SIGNIFICANCE OF FLOTATION Froth flotation as described in this chapter refers to a wet process for separating properly ground mineral particles into two or more products. It involves the separation of mineral particles from each other in a liquid pulp by means of air bubbles. Finely crushed ore is agitated in water with the addition of air or other gases. Various chemicals and oils are added to cause the selected mineral particles to attach themselves to the air or gas bubbles. These bubbles, carrying the mineral particles, rise to the surface where they are removed in a froth, while the other particles remain suspended in the pulp. The earliest flotation divided the raw material into two products: a bulk concentrate that was removed as a froth and a tailing that remained in the flotation machine. The froth usually contained the valuable constituents. The successful application of such a process depended on the recovery of a single concentrate from which one or more valuable constituents could be recovered by a chemical or smelting process. With the advance of the art, however, the principle of selective flotation, by which two or more relatively pure products could be recovered from complex raw materials, was evolved. Other chapters in this volume describe the developments during the last 50

Jan 1, 1962

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks' and to the precipitation of second phase particles,2'3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these '(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

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

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

Jan 1, 1964

By 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 Arthur Knapp

NEARLY every technical man is called upon at some time in his life to deliver a paper before a technical audience or to write a technical paper for publication. It is not necessary to be an accomplished public speaker to deliver a technical paper successfully; it is only necessary to bear in mind a few obvious points. Poorly presented papers are nearly always the result of a few errors of deportment, but they are vital and at the same time so obvious that they are often overlooked. Experience is a good teacher but a little study and careful preparation will moderate the suffering of both an amateur speaker and his audience. An author's paper suffers, through poor delivery, in direct proportion to the suffering of his audience. The best test of a paper is to have it read aloud to the author. This will bring out faults not apparent when read silently by the author. Some of the things which will probably need correcting are improper phrasing, noneuphonic sequences, and long or involved sentences. Frequently authors write their papers in short crisp sentences for oral presentation, then rewrite them for publication.

Jan 1, 1942

By AIME AIME

A COMMITTEE of the American Railroad Association, consisting of Samuel Rea, president of the Pennsylvania System, Chairman; F. D. Underwood, president of the Erie Railroad; A. T. Dice, president of the Philadelphia & Reading Railroad; E. J. Pearson, president of the New York, New Haven & Hartford Railroad; and C. H. Markham, president of the Illinois Railroad (who was represented at the meeting by J. F. Porterfield of his system), met at the headquarters of the American Institute of Mining and Metallurgical Engineers, New York, on April 6 to assist in the Coal and Coke Committee's attempt to solve the bituminous coal problem. There was a full discussion of the questions of seasonal freight rates and the purchase by the railroads during the slack months of their winter's supply of coal. As the question of fuel supply for the railroads is in the hands of the Railroad Association, as well as the coal operators, it was vital that it should be represented at this important conference. The situation from the point of view of the mine operators was presented very thoroughly. No seasonal rates were considered necessary for the year 1920, and, as this matter requires considerable thought, it will be given thorough study and worked out in detail at a subsequent meeting.

Jan 1, 1920

By P. Bolsaitis, L. Skolnick

Vapor pressures of silver over ternary alloys of six different copper to gold ratios have been measured by means of the Knudsen effusion technique. The data obtained in the temperature range of 1330° to 1375° have been used to estimate the integral excess free energies of the ternary alloys and the activities of copper and gold. The results compare favorably to the predictions based on the electron cell model of alloys recently formulated by the authors. THE orifice effusion method for measuring vapor pressures of materials in condensed phases was first introduced by knudsen, and has since been used extensively for the determination of thermodynamic properties of condensed phases. The basis of the measurement is the effusion, through a small orifice, of vapor in equilibrium with a condensed phase. Assuming free molecular flow into high vacuum, the vapor pressure, P (in mm Hg), of the effusing species is calculated from the following equation:' where w (g) is the weight of effusing species lost during a run, t (sec) the time length of the run, A, (sq cm) the area of the effusion orifice, T ("K) the temperature at which the run is conducted, M the molecular weight of the effusing species, and k the Clausing factor, a constant that corrects for deviations from free molecular flow caused by the finite thickness of the orifice walls.17 The determination of partial and integral thermodynamic variables from vapor pressure data of ternary alloys is possible only if the vapor pressures of all but one component are negligible or can be esti-

Jan 1, 1969

By James P. Kimball

Jan 1, 1885

By L. P. Davidson

The new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, 111., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the , equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through shriver presses, which deliver the purified solution to stor- age tanks, and the copper-cadmium-zinc cake is shipped for retreatment snd recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutid'ns can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid—either as acid or as sulphate sulphur in the calcine—because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60" BC. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1944

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955