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By Michael Hoch

The phase diagrams of binary systems of some of the transition elements of Groups IV, V, and VI were used to compute the partial free energies of these elements and the free energy of formation of their Laves-type compounds. From these data, isothermal sections of ternary phase diagrams were calculated and compared with experimental results. DURING the investigation of ternary and quaternary high temperature systems formed by the transition elements of Groups IV, V and VI, the binary phase diagrams for these elements available in the literature were studied. In this study, the free energies of formation of the compounds formed in these binary systems were calculated; these values were then used to determine the general shape of the ternary and quaternary phase diagrams. Above 900°C, the transition elements of Groups IV, V, and VI are all bcc and form only Laves-type compounds in binary systems. The investigation was based on the binary phase diagrams published by Hansen.1 The Cr-Nb system was constructed from the data of Elyutin and Funke.' Several unpublished phase diagrams were taken from Schmidt'sLo and English'sl1 compilations. THE BINARY SYSTEMS valuations of the Thermodynamic Functions. Rostokers evaluated the boundaries of the (a + b) field in Ti-base alloys with a two-constant equation. The authors' interest is mainly in the center of the diagrams; therefore the miscibility gaps in the Zr-Nb, W-Cr, Ta-Zr, Ta-Hf, and Ti-W systems were used to evaluate the thermodynamic behavior of the binary systems. Lumsden's4 Equations 29.2, 32.1, and 33.1, page 287, were used for the excess integral free energy FeX, and for the excess partial free energies Fx and replaces b and b replacesP in Lumsden's notation):

Jan 1, 1962

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By J. F. Tavernelli, L. F. Coffin

The deformation and fracture characteristics of eight metals subjected to fully reversed cyclic strain ranging from 0.2 to 50 pct were investigated at room temperature. Strain-hardening characteristics unique to the interna1 structure of a particular metal were found. Complete removal of the strain-hardening effects resulting from prior deformation was brought about by subsequent cyclic strain. Further support for the validity of the inverse relationship between the plastic strain range and the square root of the number of cycles for failure is given. THE resistance of materials to cyclic plastic strain is of interest both from a fundamental and practical point of view. It is now a well-accepted fact that fatigue failure in metals is a consequence of the localized slip deformation which occurs within the individual crystals of metal.'-' Hence the failure process should be strongly dependent upon the magnitude of the gross cyclic plastic deformation of the metal under conditions where this is a measurable quantity. Therefore, an experimental investigation of metals in which the cyclic plastic strain is the independent variable should shed new light on some of the basic aspects of the problem. From the practical point of view, there are many uses for information relating to the cyclic strain resistance of metals. One is the case of thermal stress fatigue where fatigue failure can occur as a consequence of a com- paratively few cycles of thermally induced mechanical deformation. Another is the mechanical working of metals where large cyclic strains are employed. In recent years several publications have appeared relating to the cyclic-strain resistance of metals,8-11 dealing mostly with the fracture aspects where the temperature is cycled simultaneously with the mechanical strain. Some work has been reported on the cyclic-strain resistance of metals at constant temperature, again oriented more toward the fracture aspects of the problem than the deformation aspects. 12-16 The present research investigation was undertaken to obtain information regarding the deformation characteristics of several metals whose structure-property relationships were simple and straightforward under conditions of both cyclic and monotonic strain. It has been shown for example that under cyclic-strain conditions some materials will strain harden, while other materials, particularly cold-worked structures, strain soften and these effects required further clarification.8,17-19 It was also de-

Jan 1, 1960

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Jan 1, 1925

By Edward Keller

(Canal Zone Meeting, November, 1910.) UNDER the title, Labor-Saving Appliances in the Works-Laboratory, I published a paper1 in which was described how multi-manipulations, in a works-laboratory, and in the furnace-room of an assay-laboratory, can be condensed into single manipulations by applying the proper mechanical devices. For example, I now deposit in, or withdraw from, a muffle a set of 48 cupels as one unit. The front row. (8) of these. are blanks or heaters; the other 40, when they have attained the proper temperature in the muffle, are charged simultaneously with the 40 lead-buttons. Three manipulations here accomplish an operation which by the generally customary method requires 136, and this number is only limited by the size of muffle and cupels. This operation is an enlargement of what I have already described in my former paper, and Fig. I shows the improved implements. In the paper referred to I described a gold-silver bead parting-bath, which is the last of the devices used in regular sequence in practice. This bath was designated as being convenient, but was not a labor-saver properly. Fig. 2 of the present paper shows a new device. Instead of the original tray, there are now sectional holders for the test-tubes, each having a wooden handle on either end, so that the holders may be removed from the boiling bath, and the acid or water poured off from each set of tubes (in this case, 7) without waiting to cool. The tubes, held in place by clutches, as shown in Fig. 3, rest in holes in the base-strip, having a smaller diameter than the tubes. Each holder is stamped at either end with a number, so that the bath becomes further useful by permitting several men to use it at the same time without interference. Apart from the handles, the holders are made of sheet-copper. ' Trans., xxxvi., 3 to 18 (1906).

Aug 1, 1910

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

Eighty-four quaternary titanium-base alloys from the following systems were investigated: 1. Titanium-chromium-carbon-nitrogen. 2. Titanium-chromium-carbon with copper, vanadium, molybdenum, manganese, iron, or nickel. 3. Titanium-chromium-nitrogen with vanadium, molybdenum, or nickel. The tensile properties, minimum bend radii, hardnesses, response to heat treatment and aging treatment, and phase relationships of these alloys are reported. HIS paper is the third in a series describing J- titanium-base alloys. The first paper describingdescribed titanium binary alloys, and the second contained data on a large number of titanium ternary alloys. Eighty-four heats, comprising three groups of quaternary titanium-base alloys, are described in this paper as follows: 1. Titanium-chromium-carbon-nitrogen alloys. 2. Titanium-chromium-carbon alloys containing copper, vanadium, molybdenum, manganese, iron, or nickel. 3. Titanium-chromium-nitrogen alloys containing vanadium, molybdenum, or nickel. The methods of preparing, fabricating, and testing the alloys are described in the paper Binary Titanium Alloys. Quaternary Titanium - Chromiurn - Carbon -Nitrogen Alloys The properties of titanium-chromium-nitrogen and titanium-chromium-carbon ternary alloys have been described in the paper Ternary Alloys of Titanium. Because small amounts of nitrogen and carbon both appear to be somewhat beneficial, these additions have been investigated fairly completely in quaternary alloys containing chromium at the following levels of composition: 2.5, 3.5, and 5.0 pct chromium 0.25 and 0.5 pct carbon 0.1 and 0.2 pct nitrogen Mechanical Properties: The mechanical properties of these alloys are listed in table I. Fig. 1 and 2 show graphically a comparison of the tensile properties and hardnesses of quaternary alloys with those of the titanium-chromium binary alloys. Fig. 1 shows the comparison at 0.25 pct carbon, whereas fig. 2 shows the comparison at 0.5 pct carbon. It is concluded from these data that 0.25 pct carbon and 0.1 pct nitrogen are desirable additions to the 5 pct chromium-titanium base. It is further concluded that most of this improvement is produced by the nitrogen and that carbon is either harmless or mildly beneficial, at least up to 0.25 pct. Structure and Transformation Range: The effects of carbon and nitrogen on the transformation range of the titanium-chromium alloys were determined as part of the routine investigation. Additions of 0.25 pct carbon and 0.1 pct nitrogen had no appreciable effect upon the transformation range. However, the addition of 0.25 pct carbon and 0.2 pct nitrogen definitely raised the beta solvus temperature, as shown by fig. 3.

Jan 1, 1951

By C. A. Stetefeldt

In May and June, 1885, I was engaged in examining the goldores of Las Minas, in the State of Vera Cruz, Mexico, with a view of finding a cheap and efficient method for extracting the gold. The following minerals could be plainly seen in the ore : magnetite, pyrites of iron, pyrites of' copper, quartz, and garnet. Neither galena nor zinc-hlende mere visible, but the ore contained a trace of lead, and in some samples of ore from the Muertos mine, 1.19 per cent. of zinc mas found. Antimony and arsenic were not present. Native gold could scarcely be seen in specimens of' the ore, and it only appeared—mainly in extremely fine particles—after pulverizing and washing. Magnetite was in every instance the most prominent mineral, its quantity varying between 43 and 67 per cent. Determinations of copper and sulphur showed that from 3.5 to 7 per cent. pyrites of copper, and from 3 to 22 per cent. pyrites of iron were present. The gold-value of the ore varied between 0.3 oz. and 0.8 oz. per ton. I do not speak of specimens, but of average samples of large quantities of ore put through the battery. In ore that had been crushed through a No. 40 screen, the gold appeared, in part, as free gold, the rest being thoroughly mixed with the magnetite and pyrites, both minerals containing about the same percentage of gold. If this free gold was brought in contact with pure quicksilver it (lid not amalgamate readily, even if the quicksilver was charged with sodium amalgam.

Jan 1, 1886

By Douglas Bunting

In the anthracite fields of Pennsylvania, mine fires occur with more or less regularity and their existence is an ever-present hazard in coal mining. In all probability 90 per cent. of the mine fires can be ascribed directly or indirectly to the ordinary miner's open lamp. Other causes may be smoking, electrical installations, gas explosions, gas feeders, and the communication of fire to the outcrops from ash dumps, culm banks, timber and brush fires. Fires in pump rooms, engine rooms, and barns have been largely eliminated as a result of the Act of Assembly, approved June 15, 1911, which provides that all inside buildings, including engine rooms, pump rooms, barns, etc., shall be constructed of incombustible materials. Smoking of pipes, cigars, and cigarettes should be prohibited in the mines and too much care cannot be exercised in preventing fires by enforcing all rules designed for that purpose. Mine fires that involve underground fighting are invariably dangerous, and all fires, irrespective of the method pursued in extinguishing them, involve property loss and expense. Each fire generally presents a more or less original problem, dependent on the particular conditions. Generally mine fires may be divided into two classes: Those occurring in inaccessible workings and those occurring in accessible workings. The methods pursued in extinguishing or controlling mine fires are as follows: (I) direct attack, (2) smothering by sealing, (3) flushing with silt or other solids, (4) flooding with water, (5) cutting off, (6) surrounding with incombustible materials, (7) digging out by stripping from the surface. Most fires arc extinguished in their incipiency by direct attack and failure to extinguish by this method is due to late discovery, lack of water, and facilities for fighting, or improper procedure in the initial attack. Should the method first pursued be unsuccessful, careful consideration should be given in determining next the method to be adopted; then the work should be carried on as rapidly as possible and under the supervision of the most competent persons. Materials and supplies should be furnished without delay and in sufficient quantities for the work to be accomplished.

Jan 1, 1922

By E. A. Anderson

THE copper-zinc phase equilibrium diagram has been the sub-ject of many investigations. Until recently, however, the boundary of the terminal solid solution of copper in zinc (eta) has not been thoroughly investigated. This paper reports determinations of the solid solubility of copper in zinc at temperatures from 100° to 400° C., the course of the liquidus and solidus for the eta solid solution and determinations of the peritectic temperature and peritectic point for the reaction between epsilon and the melt to form eta. The liquidus of the eta phase was determined by thermal analysis and the solidus by the microscopical examination of specimens quenched from temperatures above and below the solidus. The temperature of the peritectic horizontal was obtained by thermal analysis and the com-position at the peritectic point was determined by extrapolation of the solid solubility boundary of the eta phase to the peritectic horizontal. The solid solubility boundary of the eta solid solution was investigated very carefully. Particular care was used to achieve equilibrium in the alloys at each temperature selected. The X-ray, electrical con-ductivity and microscopical methods were used in determining the solid solubility limits. The X-ray method measures the changes in the solvent lattice with increasing solute content and in this manner locates the composition of the alloy at which no further change in the solvent lattice takes place, the limit of solid solubility. The method of electrical conductivity measures the conductivity of the alloys of a graded series of compositions, whereby the solubility limit is indicated by a discontinuity in the conductivity-

Jan 1, 1934

By R. W. Waterfill

MANY existing ore deposits of valuable metals have been worked out in their upper surface levels and the continued productivity of these mines is dependent on their extension to greater depths in the earth. The maximum depths at present reached are about 6000 to 8000 ft. below the surface, with no evidence of an impoverished ore vein. These mines are widely distributed; some of the best known are in South Africa, Brazil, India and in the western sections of the United States. Among the factors which increase the difficulty of working these mines at increasing depths are hoisting, rock pressure and temperature. The manner and effectiveness with which these problems are met will, no doubt, determine in a large measure the ultimate depths to which any mine can be profitably worked. The most critical of these three factors at present is the increase in temperature with depth. The high temperature and humidity in many of these mines at present is severely detrimental to the health of the workers and greatly hampers their efficiency. Some have almost reached a condition in which the human system cannot survive. The problems involved in the cooling and ventilation of mines have all been ably analyzed and presented in previous articles. For this reason, only a resume of conditions affecting the cooling and conditioning of deep and hot mines will be given in this paper before attention is directed to possible methods of improving atmospheric conditions in the working levels.

Jan 1, 1929

By Henry M. Howe

In discussing the classification of iron to-day, we are to leave out of consideration the general division into non-malleable or cast iron and malleable iron, as to the adequacy of which no question has been raised; and to confine ourselves to the subdivisions of malleable iron. This has been classified, according to the extent to which the properties imparted by carbon are present (viz., resilience, hardness,strength, and, above all, the capacity for being hardened by sudden cooling from a high temperature), into (1) wrought iron which cannot be hardened, and (2) steel which can be hardened; and this classification I shall, for briefness, term the carbon classification. Until within a few years all authorities, both metallurgical and general, have concurred in explicitly recognizing the carbon-given qualities, and preeminently the capacity for being hardened, as the essential qualities of steel; this is laid down with clearness by every writer on the subject. For several years this old classification has not been sufficient to meet all our needs, since the genius of Bessemer, Siemens, and, I may add, Holley, has produced wrought iron which has been perfectly melted, and thus freed from certain mechanical adhering impurities. This causes what we call homogeneousness for want of a better word, and gives rise to many important qualities which the old wrought iron had not; qualities universally recognized, though not readily described. I shall, for briefness, style them the fusion qualities, and a classification based on them, a fusion classification. These qualities render the new product so vastly superior, for most purposes, to the wrought iron formerly known, that it is neces-

By Charles H. Foreman

IN JUNE 1921, the Sullivan &lining Co., owned jointly by the Bunker Hill and Sullivan Mining & Concentrating Co. and the Hecla Mining Co, started work on the development of the Star Mine. The development work contemplated called for a crosscut from the Hecla workings on the 2000 level to the Star ledge. The length of crosscut necessary to encounter the Star ledge was approximately 8900 ft. from the Hecla shaft. By using workings formerly made by the Hecla Mining Co., only about 8100 ft. of actual crosscutting was necessary. This crosscut has a direction of S 20° W and would have a tendency to crosscut any ledges in the intervening ground.

Jan 1, 1924

By AIME AIME

WITH a brilliance undimmed by hard times, the annual dinner on Wednesday evening, Feb. 17, was a complete success. More than 600 members, friends and ladies gathered early and filled the anterooms of the grand ballroom of the Commodore Hotel, while the president's reception was in progress, and then at the sound of the gong and with the music of the orchestra, rising above the happy din of conversation thronged to their seats at the tables. Following the "potage Ambassadeur"-probably to eliminate a very real hazard-the usual toy balloons appeared and a gay and lively scene, punctuated by multitudinous explosions, ensued, as the hundreds, of variously colored spheres bounced yon and hither until their gaseous existence was ended on the glowing end of a cigar or cigarette. On the speakers' dais sat C. E. Beecher, Chairman Petroleum Division; J. Vipond Davies, representative of A. I. M. E. on the Alfred Noble Prize Committee; Corbin T. Eddy, Alfred Noble Prize recipient; A.' S. Tuttle, Vice-president American Society of Civil Engineers; W. C. Mendenhall, Director U. S. Geological Survey; George C. Bateman, representing the Canadian Institute of Mining and Metallurgy; Paul D. Merica, Institute of Metals lecturer and Chairman James Douglas Medal Committee; Champion Herbert Mathewson, James Douglas Medalist; Robert E. Tally; retiring President; G. Temple Bridgman, toast-master; Scott Turner, incoming President; F. W. Bradley, William Lawrence Saunders Medalist; Fred Searls, Jr., Chairman William Lawrence Saunders Gold Medal Committee; Arthur Notman, President Mining and Metallurgical Society of. America; Robert J. Grant, Director U. S. Mint; Landon F. Strobel, Chairman New York Section; Howard Scott, recipient of Robert W. Hunt Prize; George. B. Waterhouse, Chairman Robert W. Hunt Prize Committee; F. M. Becket, Chairman Iron and Steel Division; Ora E. Clark, recipient of the J. E. Johnson, Jr., Award; Richard Peters, Jr., Chairman J. E. Johnson, Jr., Award Committee; E. C. Bain, Howe Lecturer; Sam Tour, Chairman Institute of Metals Division; and H. Foster Bain, Chairman. Charles F. 'Band Foundation Committee. ' Each was heartily applauded when introduced by Mr. Bridgman, as was Mrs. Tally, who also made a bow. The toastmaster made graceful reference in introducing Mr. Strobel, to the large part the latter had taken in planning the meeting.

Jan 1, 1932

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The times at which the first detectable amount of a phase forms at temperatures between 900° and 1800°F were determined. Both X-ray diffraction and metallography were used to detect a in highly strained filings; metallography alone to detect it in annealed bulk samples of six different types of stainless steels. The a phase was found to form in accordance with the C-type reaction curve in both austenitic and ferritic alloys. In filings of types 304, 347, and 446, a formed in a few hours, and in types 316, 309, and 310, it formed in a matter of minutes at temperatures corresponding to the knee of the C-curve. Only in the bulk type 309 steel, after 500 hr, and in the bulk type 310 steel, after as short a time as 25 hr at temperature, was n detected; in both instances at approximately the same optimum temperature as in the filings. The annealing temperature affected a phase nucleation only for the filings of type 304 and 347 steels, and for the bulk samples of type 309 and 310 steels. KNOWLEDGE of both the rate of nucleation and the rate of growth of the new phase is required for a complete description of metallurgical rate phenomena. However, data on the time for nucleation alone may frequently be useful in evaluating the tendency of commercial stainlcss steels to form s under various conditions. Very little correlated information of this type is available in the literature. Shortsleeve and Nicholson' indicate that s forms in ferritic 24, 27 and 30 pet Cr steels according to a C-type of reaction curve, and Emmanuel's' data for austenitic type 310 steel also suggest this type of solid state reaction. In addition, significant, though fragmentary, information has been given by Binder, Dulis and Smith,4 Payson and Savage,.; Guarneri, Miller, and Vawter,8 rerichs and Clark,7 Wilder,5 Lismer, Pryce, and Andrews,' Smith, Dulis, and Link,10 Dulis, Smith, and Houston," and Henry, Cordovi, and Fischer." The bearing of these data on this work is covered in the discussion. The purpose of this paper is to present such correlated data on s formation in AISI type 304 (18 pct Cr-8 pet Ni), 347 (18 pet Cr-10 pet Ni-Cb), 316 (18 pet Cr-12 pet Ni-2 pet Mo), 309 (25 pet Cr-12 pet Ni), 310 (25 pet Cr-20 pet Ni), and 446 (27 pet Cr) stainless steels. Materials and Test Methods X-ray diffraction and metallographic methods were used to determine the first appearance of the s phase in cold worked filings and in annealed bulk samples of seven steels, under various combinations of time and temperature. The rate of growth of the s particles was not determined. Commercial heats of six AISI steels and a low carbon laboratory experimental heat containing about 28 pet Cr were studied. Analyses are given in Table I. Because cold work greatly accelerates the nucleation of s particles, the relative rates of s nucleation in mechanically strained samples, i.e., filings through 120 mesh, were determined for direct comparison with those in annealed bulk alloys of the same composition.

Jan 1, 1957

By A. W. Schlechten, R. F. Doelling

Parkes' process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,' raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes' crusts by one of the authors' gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes' process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes' crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper' on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned' supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

By R. G. Knickerbocker, R. R. Lloyd, W. T. Rawles

In July 1041, the Experiment Station of the Bureau of Mines at Boulder City, Nevada, began a study of methods of producing magnesium metal from magnesium oxide, with particular emphasis upon the direct use of magnesium oxide in a molten chloride electrolyte. The program was extended to include pilot-plant study of chemical methods for the preparation of pure magnesia from dolomites and magnesites. Preliminary work on the production of magnesia from dolomite was done with the cooperation of Kobert D. Pike and the Harbison-Walker Refractories Co. These investigatipns included a cooperative arrangement whereby the Bureau tested certain steps of the Harbison-Walker-Pike process. The process finally developed by the Bureau includes the precarbonation mixing step of the H.W.P. flowsheet prepared by Mr. Pike. Two magnesium-reduction plants using MgO as a source of magnesium were being constructed in the West, and they enormously stimulated interest in various dolomite deposits as possible sources of the magnesia needed by them. This paper describes one phase of this program—the operation of a pilot plant for producing cell-grade magnesia from dolomite from Sloan, Nevada. The process developed for this purpose is an adaptation of a well-known process first proposed by Clossonl and modified by others,2"1 involving the use of calcium chloride and carbon dioxide. It is based on the following chemical reactions: MgCl2 + Ca(OH)2 = CaCl2 + Mg(OH)2 [1] Mg(OH)4 + CaCU + CO2 = MgCl2 + CaCO, + H2O [2] The first reaction proceeds almost completely to the right because of the much greater solubility of calcium hydroxide as compared with magnesium hydroxide. Under equilibrium conditions, when only the four components shown in reaction I are involved, the ratio of magnesium to calcium in solution, according to solubility-product relationship, will be: This reaction is the basis of present commercial processes for recovering magnesium from sea water and dolomite. The second reaction is, in effect, a reversal of the first reaction produced by adding COz. This reaction also proceeds nearly to completion, the solubility relationship being: Ca where P indicates partial pressure of COz, in atmospheres.

Jan 1, 1944

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By Hermann Schmalzried, Carl Wagner

UPON heating a metal oxide or sulfide in H2, first only oxygen or sulfur is removed from the surface. Thus the metal/nonmetal ratio in the oxide or sulfide increases and the thermodynamic activity of the metal increases accordingly. For the formation of metallic nuclei, a certain super saturation is necessary, i.e., the activity of the metal must become greater than unity. Once nuclei of the metal have been formed, the supersaturation is supposed to decrease. Even under steady-state conditions of a reduction process, however, the activity of the metal inside an oxide or sulfide phase must be greater than unity in order to have a driving force for the individual steps of the reduction process. As an example, consider the reduction of Ag2S with a high mobility of cations and electrons. As shown schematically in Fig. 1, the reduction process involves the following steps:&apos; 1) sulfur removal along the entire Ag2S surface in form of H2S, 2) migration of Ag&apos; ions and electrons from the Ag2S surface to nuclei of metallic silver, 3) transfer of Ag+ ions and electrons from the Ag2S phase to the metal. For a finite rate of step 3, the activity of silver in Ag2S next to the Ag2S-Ag interface must be greater than unity. Moreover, for a finite rate of step 2, the activity of silver at the gas-Ag2S interface must be still somewhat greater. Theoretical considerations lead to the tentative conclusion that at least under steady-state conditions the supersaturation will be rather low.&apos; To test this conclusion, the average activity aAg of silver in a Ag2S tablet about 2 mm thick with a diameter of 5 mm was followed as a function of time by measuring the electromotive force E of the cell Pt I Ag | Agl I Ag2S I Pt where AgI is used as a solid electrolyte in which only Ag+ ions are mobile. The activity aAg is calculated as aAg=exp(-EF/RT) Since the diffusion coefficient for transport of silver in Ag2S is very high (- 3 . l0-2 sq cm per sec),3 the average activity aAg is representative for both the bulk and the surface of the Ag2S tablet. Experiments were conducted at about 400°C. The cell was surrounded by an aluminum block in order to secure a uniform temperature and to eliminate thermoelectric effects. With the help of a potentiometer, first a potential of 0.16 v was applied to the above cell in argon in order to obtain a well defined initial state with a Ag/S ratio close to 2.000.~ Then the cell was disconnected from the potentiometer and a gentle stream of H2 was passed along the Ag2S surface. In view of the removal of sulfur in form of H2S, the electromotive force E decreased within 20 to 30 min to zero corresponding to a Ag/S ratio of 2.003 and became negative, indicating a value of aAg> 1. A representative plot electromotive force E vs time is shown in Fig. 2. The minimum of the electromotive force characteristic of the onset of

Jan 1, 1963

By J. M. Dahl, L. H. Van Vlack

STAFF: Editor, Gerhard Derge Associate Editor, Paul G. Shewman Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Post-President; Harold B. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. B. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of monuscripts is under the supervision of the following Publications Committees: Extractive Metollurgy Division: R. E. Grace, Chairman; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Healy, T. A. Henrie, R. D. Holli-day, C. E. O&apos;Neill, C. S. Sami s, A. W. Schlech-ten, and Charles Shull . Iron and Steel Division: R. D. Pehlke, Chairman; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Tuckdogon, L. H.Von Vlack, and J. M. Uys. Institute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Chairman; M. R. Achter, G. F. Bolling, J. O. Brittain, G. P. Conard, II, L. A. Girifolco. G. T. Hahn, J.P. Hirth, L. Himmel, G. T. Horne, George Krauss, C. F. Leitton, Jr., J. D. Livingston, R. D. Monning, H. M. Otte, S. V. Radcliffe, R. E. Reed-Hill, H. C. Rogers, O. Sherby, M. T. Simnod, G. R. Speich, E. A. Steigerwold, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Walton, H. W. Weart, W. W. Webb, and D. WiIsdorf. Published monthly by the American lnstitute of Mining, Metollurgicol, and Petroleum Engineers, Inc., 345 East 47th Street, New York, N. Y. 10017. Telephone PLAZA 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1965 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustrial Arts Index, and Chemical Abstracts . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 233, Number 1.

Jan 1, 1965

By AIME AIME

DATA in this report enable comparisons to be made within the bituminous coal industry and comparison as well with copper and steel in respect to capacity and overdevelopment. The conclusions reached from the data will tend to correct numerous current misconceptions. The data have been prepared by various members of the Coal and Coke Committee of the A.I.M.E., from the most authentic sources avail¬able, and cover the period 1913-1924 wherever possible. CAPACITY AND OVERDEVELOPMENT Table 1 shows statistics for the industry, mainly from the U. S. Geological Survey sources, but partly from the U. S. Coal Commission reports. The mine capacity with equipment and labor as of given date is calculated for each state by obtaining the total man days worked as reported by the operators, and dividing this figure into the total production, getting the production per man day; this figure times the number of men employed times 308 (a theoretical full working year) equals estimated full-time capacity. Two major objections are made to this method-one that the total number of men employed is used instead of the number actually working, and the other that the number of days used only deducts Sundays and five holidays. Covering the first, the same number of men is used in estimating capacity as is used in actual production, and this condition exists at all times. Regarding the second, the opinion is general among coal men that 280 days is as great a figure as should be used, as it is practically impossible to keep any mine working full time at the same daily rate as when it is working part time. The capacity, as estimated on this basis, is much more nearly the true capacity, although even with present railroad efficiency this amount of coal could not be moved.

Jan 1, 1926