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By Cyril Stanley Smith, W. Earl Lindlief

A study of the mechanical properties of the alloys of copper and silver led to the discovery that the solubility of silver in copper was greatly different from that generally supposed, therefore some work was done to determine the solubility with greater accuracy than had previously been achieved. After the work had been completed, two papers were published' giving solubility figures which agreed closely with one another and with the work described herein. A detailed comparison of that work with the present will be given later. Preparation of Allots The copper used in making the alloys was electrolytic ingot of high purity. The silver was prepared by precipitation as chloride from nitric acid solution, followed by fusion of the washed precipitate with sodium carbonate and potassium nitrate. This method gives metal containing at least 99.99 per cent silver. The copper was first melted under charcoal in a small electric resistance furnace and the silver added as pure silver, it being unnecessary to make any intermediate alloys. After thorough stirring the metal was poured into a mold of suitable form. The alloys contained between 0.008 and 0.015 per cent of oxygen. Small amounts of oxide were visible under the microscope, but it is not believed this would have much effect on the results. Copper-silver alloys are notorious for segregation, consequently a few experiments were carried out to find a form of casting with as little segregation as possible. A mold 6 in. long and 1/2-in. dia. was first used, and an alloy nominally containing 5 per cent silver was cast in it, while some of the same alloy was poured directly into water to obtain the maximum rate of cooling possible. Analyses were made both on this sample and on turnings from the top and bottom of the 1/2 in. dia. cast-ing, the turnings being separated into three parts according to the position

Jan 1, 1932

By H. Papazian, Robert A. Lad

SINCE it can be shown both theoretically'' : and experimentally that disordered Cu3Au has a greater internal energy than the ordered alloy, it might be expected that its chemical reactivity would be greater. Experiments were initiated' to test this hypothesis. This note will describe some recent results obtained in the study of the rates of corrosion of ordered and disordered polycrystalline Cu3Au by aqueous FeCl., The work of Robertson' has indicated that the attack by such solutions is intergran-ular and highly orientation dependent. It was of interest to see whether the order-disorder effect was great enough to overcome the variations from specimen to specimen which would arise from this type of attack. The polycrystalline alloy specimens (0.020 in. wire, 1¾ in. long) were preannealed in ½ atm H, at 700°C for 2 hr. The subsequent heat treatments to produce order and disorder were performed in M atm He. Disordered specimens were obtained by heating at 450°C for 2 hr and quenching in water. Ordered specimens were produced by heating for 2 hr at 450°, furnace cooling to 380°, and soaking at 380°C for 80 to 90 hr. Room temperature was reached by cooling to 150" at a rate never exceeding 7" per hr, and water quenching from 150°C. The specimens so produced exhibited electrical resistivities characteristic of the two states; of the order of 11.27x10 ohm-cm for the disordered, and 4.28x10 ohm-cm for the ordered specimens. The corrosion rates were studied at 30°C in ferric chloride solutions of several concentrations (?,¼, 1.5, and 1 molar). The specimens were attached to a stirrer during the tests. Tests were interrupted at intervals, and the specimen weight change was determined after washing and drying. Analysis of the solutions showed that the attack was limited to the copper. The higher corrosion rate for the disordered alloy, as illustrated in Fig. l, is typical of the results obtained. The effect of variation in ferric chloride concentrations is indicated in Table I for typical specimens. The variations in the ratio of reactivity for disordered and ordered specimens at the different concentrations are within experimental error, and the best value is estimated to be near 1.4. The experimental variation was due in part to the mode of attack, as mentioned, and in part to the fact that films were formed on the specimens under some conditions. Electron diffraction patterns of the films were very complex and indicated the presence of metallic iron, as did chemical analysis. In an attempt to eliminate the difficulties arising from the mechanism of attack, single crystal specimens were used. A greater reaction rate was again measured for the disordered specimens, but the reproduci-bility was no better than that for the polycrystalline metal. This would indicate that film formation was primarily responsible. It was concluded that the reaction with aqueous ferric chloride served to demonstrate that the reactivity of disordered Cu3Au is greater than that of the ordered alloy. However, the difficulties with film formation did not permit determinations of a precision great enough to warrant extension of the study to partially ordered alloy systems.

Jan 1, 1957

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By Richard Moldenke

Note.—At the request of the American Society for Testing Materials, this paper wau presented at the New York Meeting, February, 1923, in connection with the "A. S. T. M. Tentative Specifications for Foundry Pig Iron" and The Physics of Cast Iron and Its Bearing on All Cast-iron Products and Specifications for Cast Iron," by William R. Webster. The discussion of this paper was not published by the Institute, having been referred to the American Society for Testing Materials, as these papers were again presented for discussion at the meeting of that Society at Atlantic Cit;, June, 1923. The result of these discussions is shown in the following abstract from the Committee A3 report on cast-iron specifications: During the past year, the adaptability of the tentative specifications for pig iron for the steel and the malleable foundry, in addition to the iron foundry proper, have been studied and suitable changes and rearrangements are being made which appear to cover the situation properly. In spite of the experience of foundrymen to the contrary, there is a persistent call from consumers of castinga for defixute compositions for given lines of castings. To respond to this call for information desired by the consumer—information every modern foundryman should have and guide his procedure with—the committee has requested the Sub-committee on General Cast!rigs to take up this matter with a view of constructing tables of analyses rang? for Important lines of foundry product. These analyses ranges however, are to be given as "recommendgd practice" and not intended for actual spkcification. In this way, the consumer of the foundry product will get the information he wants; the furnace-man will be gulded in the production of his pig irons to prepare for analyses ranges which are more closely standardized and have less of "freak" requirements made by Inexperienced metallurgists; and the foundryman will not be bound by chemical requirements he knows will not work out well with his particular reglonal supphes of melting stock. Doctor Moldenke's paper is published in full as it shows clearly the good results of the Institute's work in 1895 and a comparison of the same with the present knowledge of the metallurgy of cast iron—Bradley Stoughton, Chairman, Iron and Steel Committee. In MaRch, 1895, William R. Webster contributed a carefully prepared scheme for the study of the physics of cast iron to the American Institute of Mining Engineers at its Florida meeting. This summary of the interrelation of the chemical and physical characteristics of cast iron with the operations of daily foundry practice caused a wide discussion of the then little understood though universally used material. Mr. Webster has requested the author to bring the subject up to date and, while glad to comply, he must pay that with all the knowledge that has been gained in the quarter century that has passed since the subject was brought to the attention of the Institute—and we now are pretty familiar with cast iron in all its aspects—there is practically noth-

Jan 1, 1923

By Richard Moldenke

Note.—At the request of the American Society for Testing Materials, this paper wau presented at the New York Meeting, February, 1923, in connection with the "A. S. T. M. Tentative Specifications for Foundry Pig Iron" and The Physics of Cast Iron and Its Bearing on All Cast-iron Products and Specifications for Cast Iron," by William R. Webster. The discussion of this paper was not published by the Institute, having been referred to the American Society for Testing Materials, as these papers were again presented for discussion at the meeting of that Society at Atlantic Cit;, June, 1923. The result of these discussions is shown in the following abstract from the Committee A3 report on cast-iron specifications: During the past year, the adaptability of the tentative specifications for pig iron for the steel and the malleable foundry, in addition to the iron foundry proper, have been studied and suitable changes and rearrangements are being made which appear to cover the situation properly. In spite of the experience of foundrymen to the contrary, there is a persistent call from consumers of castinga for defixute compositions for given lines of castings. To respond to this call for information desired by the consumer—information every modern foundryman should have and guide his procedure with—the committee has requested the Sub-committee on General Cast!rigs to take up this matter with a view of constructing tables of analyses rang? for Important lines of foundry product. These analyses ranges however, are to be given as "recommendgd practice" and not intended for actual spkcification. In this way, the consumer of the foundry product will get the information he wants; the furnace-man will be gulded in the production of his pig irons to prepare for analyses ranges which are more closely standardized and have less of "freak" requirements made by Inexperienced metallurgists; and the foundryman will not be bound by chemical requirements he knows will not work out well with his particular reglonal supphes of melting stock. Doctor Moldenke's paper is published in full as it shows clearly the good results of the Institute's work in 1895 and a comparison of the same with the present knowledge of the metallurgy of cast iron—Bradley Stoughton, Chairman, Iron and Steel Committee. In MaRch, 1895, William R. Webster contributed a carefully prepared scheme for the study of the physics of cast iron to the American Institute of Mining Engineers at its Florida meeting. This summary of the interrelation of the chemical and physical characteristics of cast iron with the operations of daily foundry practice caused a wide discussion of the then little understood though universally used material. Mr. Webster has requested the author to bring the subject up to date and, while glad to comply, he must pay that with all the knowledge that has been gained in the quarter century that has passed since the subject was brought to the attention of the Institute—and we now are pretty familiar with cast iron in all its aspects—there is practically noth-

Jan 1, 1923

By Peter Tegart

The discovery of gold in the Toodoggone River area is credited to Charles McClair who mined placer deposits in 1925, reportedly valued at $17,500. After he and his partner went missing in 1927, efforts to relocate their workings resulted in the formation of Two Brothers Valley Gold Mines Ltd. in 1933, in which the legendary Grant McConachie (first president of CP Air) played an active role. This was the age when the prospector first utilized the airplane to reconnoitre remote areas. What greeted the observer from the air was an area rich in orange and yellow colours characteristic of gossans formed by the oxidation of sulphides. However, Samuel Black, a Hudson Bay Company fur trader, had also noted in his diary as early as 1824, the unusual and many gossanous colours in the headwaters of the Finlay River. These gossans, coupled with white limestone bluffs and the presence of placer gold, attracted the first reconnaissance of the area by Cominco in 1929. Cominco was ever active in remote areas at this time. They staked and worked several base-metal showings hosted by limestone at the margins of intrusive stocks. These early workers also obtained erratic high gold assays from chalcedony float samples found in creeks draining into the Toodoggone River. However, because the samples gave inconsistent assays, no concerted effort was made to locate their source. Except for the occasional horse-supported prospecting party of the late 1940s and early 1950s, the area did not receive much attention until 1968. Work until this time focused on the base metal lead-zinc showings which contained attractive silver credits. Gold was not an attraction because of the set price established by the US government. The late 1960s saw the northward expansion of porphyry copper exploration into the Toodoggone. A program of gossan soil sampling (gossans which had attracted the early workers) was carried out by Kennco Explorations (Western) Ltd. in 1966-1967. They analysed for base metals in the field, using a cold extraction method. The Kemess copper- gold prospect was staked as a result of anomalous copper values from this early geochemical program. In 1968, Kennco continued the program of silt traversing and field geochemical testing. The samples were further subjected to multielement analysis consisting of copper, molybdenum, lead, zinc, cobalt, nickel, and silver at Kennco's North Vancouver laboratory. Several anomalous creeks, high in combinations of copper, molybdenum, and silver, were outlined. Some initial soil grids were also established. The fall of 1969 saw the return of Kennco prospector Gordon Davies and geologist Bob Stevenson to check out a well-defined molybdenum, scattered copper and silver anomaly in soils from a grid on the Chappelle claims. The subsequent analysis of several selected quartz felsenmeer floats yielded one assay which ran in the order of 0.25 kg/t (8 oz per st) gold and 2.2 kg/t (70 oz per st) silver. Subsequent trenching on the Chappelle claims exposed the source of float in a 4- m (134) wide vein of high grade gold-silver mineralization. These results led quickly to the realization that the district had precious metal potential. Subsequent exploration in the period 1969-1974 by Kennco resulted in the discovery of most of the gold and silver occurrences on the Chappelle and Lawyers properties. Several other gold and silver occurrences were found in this district by Cordilleran, Cominco, and Sumitomo, working the district during this period. Conwest optioned the Chappelle in 1973 and explored underground by adit entry as part of a one-year program. In 1974, Du Pont of Canada Exploration Ltd. optioned the Chappelle claims and in March 1980, using reserves developed on the A vein, placed the Baker mine into production at a rate of 90.7 Vd (100 stpd). The Amethyst zone on the Lawyers property, 8 km (5 miles) north of Chappelle, was found in 1973 by Kennco using continued, persistent followup prospecting of silver silt geochemical anomalies. A silt anomaly in the order of 3.4 ppm silver occurred in a stream flowing 300 m (984 ft)

Jan 1, 1985

By R. S. Shoemaker, F. W. McQuiston

SOUTH AFRICAN MILLING PRACTICE All modern South African gold plants operate primarily on the principle of exposing the gold particles in the ore by fine grinding and then cyaniding the total pulp. Although there are minor variations and occasional depart- ures from established practices among the fifty gold mines in South Africa, the normal plant operations proceed as follows. After removal of waste rock by hand sorting (15Y0 on average) the ore is crushed in cone crushers to minus 1/2 inch and then ground to approximately 75% minus 200 mesh by milling with either rod, ball or pebble mills as primary units and pebble mills for the secondary grind. Classification in both circuits is almost invariably conducted with 20" cyclones of 30" or larger diameter. Gravity concentration in the milling circuit followed by barrel amalgamation of the concentrates is practiced in 70Y0 of the plants, particularly where the ore grade is high. A slightly better overall recovery is obtained than with direct cyanidation, but additional handling is involved. Johnson cylinder s , plane tables or belt concentrators, all lined with suitable types of molded rubber riffles, are used for this purpose. At all mines, cyanidation is the main process, usually conducted by continuous treatment in Pachuca tanks and pulp separation with rotary drum filters. Cyanide solutions contain about 0.0 1570 NaCN and require a protective alkalinity of 0.02070 CaO. Precipitation of the gold from cyanide solution is exclusively by zinc dust and lead nitrate using the Merrill-Crowe system in conjunction with Stellar pressure filters. The zinc precipitate is smelted, generally after a preliminary concentration by sulfuric acid, in electric furnaces, mostly submerged arc types, with a silica and borax flux, yield- ing a bullion of 8870 gold, 9% silver, and 370 base metals. The gold content of the ore varies between 0.20 and 1.0 oz Troy per short ton and extraction efficiency ranges from 9570 to 9870. In general, 4070 of the gold output is recovered by amalgamation and 6070 by cyanidation; but in some cases, it is entirely by cyanidation. Flotation has not been adopted for gold extraction as it has not proved as efficient as cyanidation. It is, however, often applied to ores containing higher than 1% sulfur for the recovery of pyrite for sulfuric acid production. On the eastern side of the Witwaters rand Basin, "run-of -mine milling” was introduced in 1960 and in three of the four mills in this area both sorting and crushing have been eliminated. The ore received from the shafts is conveyed to storage silos and then fed by Williamson automatic feed controllers to pebble mills ranging from 12 to 14 feet diameter, and 16 to 20 feet long. The pebble mills operate in closed circuit with 42 inch cyclones and the slime produced is thickened and cyanided in the conventional manner. No selective

Jan 1, 1975

New Jersey Zinc Co. - The Mines Franklin-Sterling Friedensville Development Austinville Ivanhoe Development Eagle Mine Hanover

Jan 12, 1953

The 139th meeting* of the American Institute of Mining and Metallurgical Engineers was held at New York, February 17 to 20, 1930, the attendance totaling approximately 1800. The meeting consisted of the annual business session, 34 technical sessions at which were presented 166 papers, two meetings of the Board of Directors, two meetings of Section Delegates, two formal lectures and one special lecture, five group dinners and one group luncheon, luncheon daily for members and guests, fourteen committee meetings and conferences, the President's reception, the dinner-dance, an informal dance, a smoker, an exhibition of rare minerals and metals, two meetings of the Woman's Auxiliary and a special program of entertainment for the ladies. The Petroleum Division held seven sessions, including two general sessions featuring, respectively, a symposium on unit operation of oil pools and reports on developments in the petroleum industry during the previous year. The Iron and Steel Division held four sessions, at one of which Dr. Zay Jeffries delivered the Howe Memorial Lecture, the title of which was "The Future of the American Iron and Steel Industry." The Institute of Metals Division held six sessions, including two devoted to a symposium on the Melting and Casting of Metals, and the general session at which Dr. S. L. Hoyt delivered the annual Institute of Metals Lecture. The title of his lecture was "Hard Metal Carbides and Cemented Tungsten Carbide." The Coal and Coal Products Committee devoted one session and the greater part of another to Coal Classification and at a third session organized as the Coal Division of the Institute. The Committees on Mining Methods and Ground Movement and Subsidence each held a session, besides which they met jointly. Sessions were held by other Technical Committees as follows: Nonferrous Metallurgy, 1; Geophysical Prospecting, 2; Nonmetallic Minerals, 2; Milling Methods, 1; Rare Minerals and Metals, 1; Mining Geology, 2; Mine Ventilation, 2; Engineering Education, 1. At the annual business meeting on February 18, the following ticket was elected, and the reports of the President, Treasurer and Secretary were presented: William H. Bassett, President; Scott Turner, Vice-president; Henry Krumb, Vice-president; R. C. Allen, Cadwallader Evans, Jr., John M. Lovejoy, John A. Mathews and Milnor Roberts, Directors. At an executive session of the Directors on Tuesday afternoon, H. A. Guess was elected Vice-president to fill the vacancy created by the

Jan 1, 1930

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2'3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,' and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the recrystallization temperature of titanium has been investigated. All additions, except columbium and tungsten, raised the recrystallization temperature. A correlation is obtained between the logarithm of the absolute rate of change of recrystallization temperature with atomic percent solute and the number of uuter d shell electrons attributed to the free atom of the solute element in its ground state. The work of Abrahamson, et aL.1-6 on dilute binary solid solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and recrystallization temperature. It is shown in these studies that the number of outer s and d electrons in the solute are of prime importance in determining the absolute rate of change of recrystallization or transition temperature with composition. Furthermore, the limit of initial linearity (in the curve of recrystallization temperature vs at. pct solute) has been shown to be a function of the number of d shell electrons in the solute for dilute iron- and vanadium-base alloys. To date no complete systematic recrystallization study of dilute binary titanium base alloys has been made. This study together with that of zirconium base alloys 6 will provide the data for the comparison of the effect of the same solutes upon two solvents with the same number of outer d shell electrons.

Jan 1, 1962

Three. meetings for the presentation and discussion of papers were held in 1914, as follows: The 107th Meeting, including the Annual Business Meeting, in New York, Feb. 16 to 19; the 108th Meeting, Aug. 10 to 14, in Salt Lake City, and the 109th Meeting, Oct. 8 to 10, in Pittsburgh, Pa., under the auspices of Iron and Steel Committee, Committee on Coal and Coke, Committee on Petroleum and Gas, Committee on Non-Metallic Minerals. Local Sections &apos; Three new local sections were established during the year, namely; / Pennsylvania Anthracite Section, Chicago Section, and Utah Section.

Jan 1, 1917

As a result of Engineering Council&apos;s request to the Director of the Census, the National Service Committee has been successful in effecting a reclassification of engineers so that all technical men will be listed as such and they will be separate and distinct from the non-technical engi-neers. Thus, the next census will bring an enumeration of all technical engineers together as one unit under the main headings of civil, mech-anical, electrical and raining; architects also will be enumerated separately. This will enable the engineering profession, the Government or any other interested organization to know exactly how many technical men there are in the United States and in each state. The enumeration will also include non-technical engineers, except that there will be no such heading and in order to get the totals of non-technical men all of the various grades of this classification would have to be sorted out and added.

Jan 12, 1919

By W. R. Ingalls

DURING 1921, the Oklahoma mines dominated the American zinc-producing industry. They comprised the only group that could produce under the adverse conditions that prevailed. At the beginning of 1921, there were about 34 mills in opera-tion in the Tri-state District, out of a total estimated variously at 150 to 200, and these were producing at the rate of about 5000 tons of blende concentrate per week. At the end of 1921, there were about 50 mills in operation. The Tri-state District rates about 80 men to the mine and mill, on-the average. SMELTING The zinc smelters-in 1921 experienced a disastrous year. All of them operated at greatly reduced capacity and probably most of them suffered loss in operations. Smelting costs came down to a considerable extent by virtue of drops in the price for coal, wage reductions and more efficient work, but these ameliorations were insufficient to enable the smelters to come out even. In the Illinois fields, wages at the end of 1921 had been reduced about 37 per cent. from the peak (middle of 1920), but coal continued to be very dear. The operation of works at a low rate of their capacity was a discouraging and expensive condition. At the end of 1921, the zinc-smelting capacity ,of the United States was as follows:

Jan 7, 1922

By S. C. Hollister

An evaluation of the function of the engineer, so that means whereby education can best serve his needs can be adopted.

Jan 2, 1950

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By E. DeGolyer

The problem of good engineering practice and. of good conservation practice in oil production is that of keeping gas in solution. This can best be done by producing a field as a water-drive field. Some degree of water drive is believed to be present in most fields but in the past most fields have been produced too rapidly to allow water drive to be effective. Ultimate recovery should be So per cent greater for fields produced by water drive over that from gas-expansion fields. Wide spacing will permit fields of low-degree water drive to be produced effectively as water-drive fields. INTRODUCTION NEGLECTING all the complicated scientific and technical argument that leads to the conclusion, the solution of the problem of good production practice, of good engineering practice, and of good conservation practice in oil production is to keep gas in solution. This can best be done by producing fields at a rate low enough to make effective the water drive, which exists, it is generally believed, to a degree great enough to be made effective in more than 80 per cent of the fields of the United States. Oil is being so produced in the Ten Section field of California; the Hobbs field of New Mexico; the Yates, Hastings, Friendswood, Anahuac fields and the main sand of the Conroe pool, in Texas; the Magnolia pool in Arkansas, and doubtless in many other pools. The measures of success in the efforts to achieve the solution of the problem are the maintenance of bottom-hole pressure and the prevention of an increase in gas-oil ratio. Some decline from the original bottom-hole pressure and the production of some gas are essential. A pressure gradient from the reservoir to the well is necessary and at least as much gas must be produced as that in solution in a barrel of oil. Once the optimum pressure and the gas-oil ratio have been established, they should be maintained. How common is water drive in oil and gas pools? General opinion is that some degree of water drive is almost universal. Theoretically, this conclusion appears to be a sound one. According to our present understanding of the processes of sedimentation, we would expect to find all sands or sandstone charged with connate water unless it had been displaced by some other fluid, such as fresh water percolating into the beds at the outcrop, or oil and gas, or gas only, in reservoirs. The fact that the original pressure of the fluid system in most reservoirs is approximately that of the hydrostatic head of water for the corresponding depth indicates that the sands are charged with water, and common experience in drilling into the extensions of the porous zones beyond the reservoir is to find them watercharged. The very fact that oil and gas pools have substantial pressures in their original undisturbed state indicates either that a reservoir is a rigid, closed system, a con-

Jan 1, 1941

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.&apos; This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By Charles P. Williams

THE determinations of the specific gravities of a number of samples of lead produced in Missouri, which form the subject of this note, were undertaken with the view of ascertaining if any approximation to the purity of such leads could be reached in this manner. The results would seem to indicate that, whatever value the method may have in the case of the crude and more impure

Jan 1, 1877