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By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,'-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker's data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963

By L. D. Woodworth, E. E. McGinley

During the past several years has occurred what, in the light of future events, may aptly be called the rebirth of the acid Bessemer process. The increased attention given to the technical and metallurgical details involved in the production of Bessemer steels has been exceedingly fruitful, and indicates the value of further research and p1ant development. In times like these, when the steelmaking capacity of the country is operating at a maximum rate to supply materials for the national defense program, it behooves the Bessemer operator not only to strive to increase production but also to maintain a high standard of quality. The opportunity is ripe, it seems, to recapture fields of application once considered the birthright of Bessemer steels, but supplanted in recent years by open-hearth grades. This involves cooperation all along the line, from the blast-furnace operator to the metallurgical contact man and salesman. The metallurgist's part in this program involves the study of the many steelmaking variables and the measures necessary to ensure constancy in the finished product. It is equally important that the knowledge gained be disseminated widely to ensure the wise application of Bessemer steels in new fields. The merits of Bessemer steels for certain work are well understood. The combined properties of good weldability, machinabil-ity and stiffness are unique and fully explain the strong entrenchment of Bessemer steels in certain fields; e.g., skelp for small butt-weld conduit, screw steels machined in automatics, and certain tin-plate applications. It is the purpose of this paper to review briefly the physical properties of Bessemer steels as contrasted with those of open-hearth steels, to discuss control measures now employed in the making of Bessemer steel, and to consider the advantages derived from the use of these control measures. Physical Properties oF Bessemer vs. Open-hearth Steels A number of Bessemer blows and open-hearth heats were tested for tensile strength, ductility and impact strength. The steels selected were confined to sections from 3/4 to 1 1/4-in. diameter, inclusive, and the carbon content covered was sufficient to yield parallel ranges in ultimate strength for the comparison. Other factors, such as the extent of deoxidation of the steel and variations in chemistry, were kept as comparable as possible. Machined test pieces of 0.505-in. diameter with an 8-in. gauge length were pulled. The data obtained are shown in Fig. I, ultimate strength being plotted against carbon content. This graph shows that for equivalent carbon content Bessemer steel has on the average 15,000 lb. per sq. in. greater tensile strength and, conversely, for the same tensile strength Bessemer steel requires on the average 0.14 per cent less carbon. The average phosphorus content for the Bessemer steel was 0.090 per cent,

Jan 1, 1941

By E. E. McGinley, L. D. Woodworth

During the past several years has occurred what, in the light of future events, may aptly be called the rebirth of the acid Bessemer process. The increased attention given to the technical and metallurgical details involved in the production of Bessemer steels has been exceedingly fruitful, and indicates the value of further research and p1ant development. In times like these, when the steelmaking capacity of the country is operating at a maximum rate to supply materials for the national defense program, it behooves the Bessemer operator not only to strive to increase production but also to maintain a high standard of quality. The opportunity is ripe, it seems, to recapture fields of application once considered the birthright of Bessemer steels, but supplanted in recent years by open-hearth grades. This involves cooperation all along the line, from the blast-furnace operator to the metallurgical contact man and salesman. The metallurgist's part in this program involves the study of the many steelmaking variables and the measures necessary to ensure constancy in the finished product. It is equally important that the knowledge gained be disseminated widely to ensure the wise application of Bessemer steels in new fields. The merits of Bessemer steels for certain work are well understood. The combined properties of good weldability, machinabil-ity and stiffness are unique and fully explain the strong entrenchment of Bessemer steels in certain fields; e.g., skelp for small butt-weld conduit, screw steels machined in automatics, and certain tin-plate applications. It is the purpose of this paper to review briefly the physical properties of Bessemer steels as contrasted with those of open-hearth steels, to discuss control measures now employed in the making of Bessemer steel, and to consider the advantages derived from the use of these control measures. Physical Properties oF Bessemer vs. Open-hearth Steels A number of Bessemer blows and open-hearth heats were tested for tensile strength, ductility and impact strength. The steels selected were confined to sections from 3/4 to 1 1/4-in. diameter, inclusive, and the carbon content covered was sufficient to yield parallel ranges in ultimate strength for the comparison. Other factors, such as the extent of deoxidation of the steel and variations in chemistry, were kept as comparable as possible. Machined test pieces of 0.505-in. diameter with an 8-in. gauge length were pulled. The data obtained are shown in Fig. I, ultimate strength being plotted against carbon content. This graph shows that for equivalent carbon content Bessemer steel has on the average 15,000 lb. per sq. in. greater tensile strength and, conversely, for the same tensile strength Bessemer steel requires on the average 0.14 per cent less carbon. The average phosphorus content for the Bessemer steel was 0.090 per cent,

Jan 1, 1941

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

By Adrien Berton

For nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Pas, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1937

By S. S. Clarke

Late in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of Jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of Jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1949

By P. M. Robinson, M. B. Bever

The heats oj formation at 273°K of the compounds CdTe, I)z2Te, InTe, In2Te3. In2Te5, SrzTe, and PbTe have been rleasrred in a liquid metal solutiotz caloritrete? 1.t1itlz bismuth as solvent. The?, are iterpretecl in yelation to tlze stability and bonding of the cott/pozltzds. Tile heats of fusion atzd the melting- points of tlze cotlzpounds InTe and Itzz,Te3 1lcti.e been measured in a cotrslant-temperature gradient calorimeter. The entropies of fusion are disc,ztssecl in YIIIS 01. the degree of order in the solid at the melting point. THE heats of formation of the tellurides of cadmium, indium, tin, and lead have been measured as a continuation of research on the thermodynamic properties of compounds of tellurim.' The tellurides of these metals were selected with a view to examining the relation between the heat of formation and the position of the metal in the periodic system. The elements cadmium, indium, and tin are in the same period and tin and lead are in the same group of the periodic system. The tellurides of indium are of special interest because four compounds, In2Te, InTe, In2Te3, and InzTe5, occur in this system. The available information on the heats of formation of the compounds investigated consists of values for CdTe, SnTe, and PbTe derived from electromotive-force measurements,J a value for CdTe obtained by tin solution alorimetr, and values for InTe and In2Te3 determined by combustion calorimetry.5 These values, however, refer to various temperatures ranging from 273' to 673°K and some of the reported error limits are large. Liquid metal solution calorime-try may be expected to yield more accurate values for the heats of formation than electromotive-force measurements or combustion calorimetry. The heats of fusion and the melting points of the compounds InTe and In,Te3 were determined in a constant-temperature gradient calorimeter. No published information appears to be available on the heat of fusion of these compounds. The results reported here give an indication of the degree of order in the solid compounds at the melting point. 1) MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Samples of the compounds SnTe and PbTe were obtained from the Westinghouse Research Laboratories and samples of the compound InTe from Lincoln Laboratory, Massachusetts Institute of Tech- nology. Additional samples of the compounds InTe, SnTe, and PbTe and samples of CdTe, In2Te, In2Te3, and In,Tes were prepared from 99.995 pct Cd (Baker Chemical CO.), 99.999+ pct In (American Smelting and Refining Co.), 99.99 pct Sn (Baker Chemical Co.), 99.999+ pct Pb (Fisher Scientific Co.), and 99.999+ pct Te (American Smelting and Refining Co.). Stoichiometric amounts of the component elements were melted in sealed, evacuated Vycor tubes. The melts were held at approximately 100°C above the liquidus for about 16 hr and shaken repeatedly. The melts of the compounds In2Te and InzTe5, which form by peritectic reactions, were quenched into iced water. The melts of the other compounds, which have congruent melting points, were slowly cooled to room temperature. The samples were then annealed for 5 days at approximately 50°C below their respective solidus temperatures. Metallographic examination did not reveal any evidence of second phases or segregation. At least two batches of each compound were prepared. Samples from each batch were used in determining the heats of formation and, in the cases of InTe and In,Te3, the heats of fusion. The Heats of Formation. The heats of formation at 273°K of the compounds were measured by metal solution calorimetry with liquid bismuth at 623" as solvent. In this technique, the heat of formation is determined from the measured heat effects on dissolution of the compound and of a mechanical mixture of the component elements. The difference between these heat effects adjusted for changes in the composition of the bath gives the heat of formation at the temperature from which the samples are added to the bath (273°K). The experimental technique and method of calculation have been described in detail elsewhere.= It should be emphasized that the reported heats of formation depend on the thermodynamic data used in calculating the heat effects for the calibration additions. In the present investigation, the calorimeter was calibrated by adding pure bismuth at 273°K to the bismuth bath at 623°K. The reported heats of formation are based on a value of 4.96 kcal per g-atom for the difference in the heat contents of bismuth at 623" and 273". If a new value for this quantity becomes available, the reported results may be adjusted in direct proportion. The concentration of solute in the bath at the end of a calorimetric run did not exceed 1.7 at. pct and was usually less. In this range, the heat effect on dissolution of the solute was a linear function of the concentration of solute. In determining the heats of formation of the compounds in the system In-Te, a few runs were carried out in which two neighboring compounds such as InTe and In,Te3 and the corresponding mechanical mixtures of the components were added to the calorimeter. The

Jan 1, 1967

By Eben E. Olcott

The Mine.—For some years attention has been drawn to the copper deposits of the Appalachian range of mountains, and especially to those in that portion crossing the corners of Virginia, North Carolina, and Tennessee. Certain it is that in many places in this locality available deposits of copper await the miner, and one after another are being opened and worked. The parts of these three States alluded to are but sparsely settled, and communications are insufficient to meet the demand for transportation. Railroads are wanted, as the existing wagon roads are unfitted for heavy hauling; these circumstances increase very much the difficulties in the way of mining enterprises. Notwithstanding this, the success of some of the mines of this section is an established fact, and Ducktown has for some years held a high rank among the copper-producing localities of the United States. of all these deposits, however, none is more interesting or more deserving of attention than the one now under consideration. The works of the Ore Knob Copper Company have been energetically pushed forward, since the reopening of the mine, in the spring of 1873, by Mr. J. E. Clayt,on, the superintendent and one of the chief owners of the property, and if one thing more than another can insure success it is the combination in this gentleman of rare business capabilities with the deepest personal interest in the prosperity of the undertaking. The copper vein at Ore Knob* is a clearly defined fissure traversing the gneissic rocks of Pre-silurian age in a direction 61' east of north.

By Andrew Cosgarea, William R. Upthegrove, Morteza Mirshamsi

The capillary-reservoir technique was used with lead-210 and cadmium-115m to determine the self-diffiLsion coefficients of both cadmium and lead in the liquid binary Cd-Pb system. The self-diffusion coefficients of pure cadmium and pure lead were obtained and were compared with the theoretical predictions. Good to excellent agrement between the experimental and predicted values was obtained. The self-diffusion coefficients of cadmium were tneasuved in alloys containing 2.50, 9.13, 17.40, 31.00, 45.00, 69.00, and 97.00 lot pct Cd by determining- the amount of cadniiutn-115m which diffused out of a small-bore capillavy into an infinite reservoir during- a given time peviod. Sinzila7-measurements were made with lead-210 to determine the self-diffusion coefficients of lead in these identical alloys. Diffusivities were determined from measurenzents performed in the temperature interval of 290" to 480°C. The results were correlated with the Ar-vhenius equation, and the maximum variation of the equation parameters (Q and Do) was also inrestigated . THE theory of diffusion in liquids, particularly liquid metals, is relatively undeveloped in contrast to that for the gaseous and solid states. Although the practical application of liquid metals as heat-transfer media has become increasingly important, few liquid-metals systems have been investigated. Experimental data of fundamental significance in this field are not readily obtained, which may explain but not justify the present lack of knowledge. What work has been completed is primarily restricted to liquid diffusion of pure metals; little work has been done in liquid-metal diffusion of binary mixtures. A review of liquid-metal diffusion theory and research is available elsewhere.1-4 In an effort to add to the knowledge of liquid-metal systems and to increase the basic understanding of the diffusion process in liquids, a study of diffusion in the binary-liquid system, Cd-Pb, was undertaken. The capillary-reservoir technique5 was employed to measure the self-diffusion coefficients of cadmium and lead in molten binary alloys. Measurements were made with seven selected compositions and over a temperature range from 290° to 480°C. The experimental apparatus consisted essentially of the following items: constant-temperature bath, diffusion cells, capillaries, capillary-filling device, and a radioactive tracer counting system. EXPERIMENTAL APPARATUS Constant-Temperature Bath. A cylindrical steel vessel, 8 in. in diam and 15 in. deep, surrounded by an insulated heating coil was used with a sodium-potassium nitrate salt mixture heating medium. The bath was maintained slightly below the desired control temperature by the furnace-heating element; and a 250-w heater, actuated by a Bayley proportional temperature controller, was utilized for the final control of the temperature. A constant-speed mixer stirred the salt to insure a uniform temperature within the bath. Four calibrated Chromel-Alumel thermocouples were placed at various positions in the salt bath to verify the absence of temperature gradients. The observed temperature variation during any diffusion run was less than 0.l°C. The entire furnace assembly was mounted on four shock absorbers to exclude building vibrations and the stirrer propeller blades were adjusted so not to induce vibrations within the reservoir. A schematic diagram of the furnace and the constant-temperature bath is shown in Fig. 1. Diffusion Cell. The diffusion cells and associated parts were the same, except for slight modification, as the one used by walls1 in this laboratory, and are shown in detail elsewhere.' A graphite crucible, 4 in. long and 40 mm (1-1/2 in.) ID, enclosed in a 60-mm (2-1/4 in.) Pyrex tube cell about 18 in. long, was used as a container for the melt. The reservoir (molten alloy in the graphite crucible) was usually about 2 to 2-1/2 in. deep. Graphite was used because of its satisfactory nature as a refractory material and the low solubility of carbon in molten Cd-Pb alloy.677 The Pyrex cell was closed at the bottom and fitted at the top (open end) with a 2-in. Dresser coupling. A brass flange was welded to the top of the coupling. The upper part of the diffusion assembly was bolted to this flange with an O-ring seal. The lower part of the diffusion cell was supported in a 3-in. brass cylinder which was open to allow for circulation of salt around the cell. The top assembly consisted of two synchronous motors, a drive shaft, a thermocouple well, and controlled-atmosphere inlets and outlets. One motor was used for rotation of the capillaries at a rate of 1/2 rpm in the reservoir during the diffusion run. The other motor was used for the vertical positioning of the capillaries and the capillary holder by means of a simple screw drive. The capillary holder and drive assembly were lowered into the reservoir for the run and raised after the desired diffusion time at a rate of approximately 0.4 in. per min. Capillary holders were made of graphite. These

Jan 1, 1967

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By P. T. Gallagher, W. A. Oates

THE partial excess entropy of interstitial solutes in metals, SXS , has usually been interpreted as being principally vibrational ever since the initial statistical treatment of hydrogen in metals by Fowler and Smith-ells. The vibrational entropy is considered being due to the optical modes of the light interstitial atom. Little attention has been given to the magnitudes of the values of SXS'. Leiser and Witte2 and Ebisuzaki and O'Keeffe3 have noted that for hydrogen in metals Si is approximately constant for different metals. On the other hand if it is assumed that the interstitial solute is an isotopic defect then, as shown by McLellan, SXS should vary from metal to metal as follows: where S is the standard entropy of the solvent and Mi, M, are the masses of the interstitial and solvent atoms. respectively. Fair agreement with this equation was found for oxygen in silver and nitrogen in iron4 and for carbon in iron.= Ln a subsequent analysis of metal- hdrogen systems McLellan' found a variation of $' from metal to metal but not in a manner expected from the isotopic impurity equation. However, a possible correlation between the energy of solution, Ei, and sf was noted. Similar correlations have been noted for certain dilute substitutional solid Solutions 7, 8 and recently Kubaschewski 9 has demonstrated a correlation between integral heats and ex-

Jan 1, 1970

By C. J. Guntner, R. P. Reed

A commercial 18Cr-8Ni iron alloy (AISI 304L) was examined in tension at 300°, 76°, 20°, and 4°K. Continuous stress-strain recordings were made, X-ray analyses at periodic stress (strain) intervals were obtained, and the magnetic measurements were taken. From this data the percentage of martensitic products [bcc(a) and hcp (E)] was computed as a function of stress (strain). It was found thatup to 15 pct E phase forms at low temperntures. The amount of E formed increases to a maximum at about 5 pct strain, then decreases. This decrease indicates the additional transformation of E to a'. The total amount of E and a' was suppressed at constant stress (strain) at 4°K as compared to 76°K. It is proposed that the suppression of E and a' is associated with the decreased mobility of extended dislocations at very low temperatures. The yield strength decreased as the temperature was depressed below room temperature and then increased rapidly near 4°K. SOME ferrous alloys which are austenitic (fcc ?) at room temperature appear to be unique in that two martensitic products (hcp e and bcc a') may form on cooling to lower temperatures or on application of mechanical stress. The most common room-temperature austenitic ferrous alloys are 18Cr, 8Ni stainless steels. Most aspects of the spontaneous transformations have been previously described for these steels.' Several previous papers have described special aspects of the stress-induced transformations at low temperatures for the stainless steels, such as the existence of the hcp phase (c) after straining at 76oK,2-7 the morphology after straining using electron microscopy,7 and the decrease in E at higher strains at 76oK.4 However, for a complete representation, one must know the stress-strain characteristics and the dependence of both martensitic products on applied stress and temperature. It is the intention of this paper to provide that documentation. To accomplish this, continuous stress vs strain recordings were made at four temperatures: 300°, 76", 20°, and 4°K for annealed AISI 304L (a commercial 18Cr-8Ni alloy). At periodic stress intervals at each temperature the integrated X-ray line intensity of a selected peak for each phase (y, E, and a') was measured. In addition, photomicrographs of the strained surfaces were taken and magnetic measurements were made. The magnetic readings can be directly converted into percent a'.',e With these measurements the percentage of each phase may be plotted as a function of stress (or strain) and test temperature. It was found that up to 15 pct E phase forms upon stressing the AISI 304L alloy at low temperatures. The E percentage increases abruptly after the alloy yields, but then decreases gradually at higher stresses. The rapid increase in e at 76°K is associated with an "easy-glide" portion of the stress-strain curve. The total amount of a' + .G is suppressed below 76°K at a constant stress or strain. The yield strength decreases down to 76°K but increases rapidly below 20°K. EXPERIMENTAL PROCEDURE Tensile test specimens were cut parallel to the rolling direction from 0.1-in.-thick sheet. Continuous stress vs strain recordings were obtained at each test temperature (300°, 76o, 20°, and 4°K) using equipment and methods described elsewhere.' The specimens which were used in the X-ray analysis were stressed to successive increments of strain at each temperature, analyzed at room temperature, then restressed at the test temperature. This procedure was repeated until approximately ten X-ray analyses had been performed with approximately 1.0 pct strain increments. The specimens had a reduced section 1 in. long, 1.2 in. wide, and 0.1 in. thick. They were electro polished prior to testing and after each strain increment. Table I lists the chemical composition, grain size, and hardness for the alloy which was used. This is the same alloy for which extensive mechanical-property tests3 and morphological studies of the spontaneous transformations' have previously been made. For the low-temperature tests (76o and 4°K) below the Ms temperature the specimens were initially cooled to the test temperature, held for 1/2 hr, then warmed and X-rayed at room temperature. The results are listed in Table 11. From earlier work8 it was known that additional transformation on the second cycle would be considerably less (-0.1 pct

Jan 1, 1964

By Neil H. Cole

Cost and price inflation and financial gearing through loans are characteristic of modern resources projects. Conventional discounted cash flow and 1P.R analyses, in real terms, and without financing, have inadequacies which can yield misleading results. The degree of improvement in value for project equity owners is limited to the value of the additional tax benefit accorded through the financing instrument used. Debt financing may be low in price and value, but its priority means that the equity owners assume a higher risk, thereby increasing the cost, or price, of their capital. The cost of equity capital, or investment hurdle rate, is related to the Capital Asset Pricing Model. Distortions do occur, with inflation, due to depreciation effects, which can cause the adoption of misleading project rate of return or hurdle rate criteria. For investment decisions, the greatest accuracy possible in forecasting is essential, especially for inflation rates,

Jan 1, 1985

By J. D. Braun, C. W. Powell

Diffusion between gold and indium at two temperatures below the melting point of indium (155.4oC) was investigated. The major, component of the diffusion zone was determined to be AuIn2; the other, intermediate phases in the system occur in much narrower layers In order of decreasing layer width these are: Au9In4, AuIn, Au4In. Inter diffusion coefficients of the four intermediate phases and the terminal solid solutions lie in the range of 2.4 x 10-l3 to 1.8 x 10-11 sq cm per sec. WHEN two metals which do not form a continuous series of solid solutions interdiffuse, each phase in equilibrium at the diffusion temperature should appear as a separate layer in the diffusion zone. In the Au-In system, diffusion plays a significant part in many commercial applications, particularly where indium alloys are used as solders for electrical contacts with very fine gold wire, for estab- lishing electrical contact to thin metallic films, and for mounting metal-coated piezoelectric crystals. A knowledge of the number, extent, and type of phases which form at diffusion temperatures below the melting point of indium, 155.4oC,1 and the diffusion constants for the system would be useful for these practical applications. Of more basic significance, additional information on polyphase diffusion in a system not previously investigated would be gained. The phase relationships in the Au-In system were determined primarily by Kubaschewski and Weibke1 and are based on thermal, microscopic, and X-ray analysis, Fig. 1. There are five intermediate phases in the system having approximate compositions corresponding to the formulas: Au4ln (ß)—80.0 at. pet Au; Au3In (?)— 75.0 at. pet Au; Au9In4 (d)—69.2 at. pet Au; AuIn—50.0 at. pet Au; AuIn2—33.3 at. pet Au. Solid solubility of indium in gold at 700°C is reported as 12.64 at. pet and at 406°C as 10.36 at. pet. No solid solubility of gold in indium is reported.

Jan 1, 1964

By E. Luttgen

The substance referred to in the title is the artificially prepared basic carbonate of magnesia, a compound of the carbonate with the hydroxide. It is the "block-magnesia " of commerce, the magnesia alba of the pharmacist. Its composition, though somewhat indefinite, may usually be expressed by the formula : 4MgCO3,Mg(OH)2, 5H2O; it is found to vary slightly with the details of the method of preparation. This substance has been employed recently with much reported success, as a non-conductor of heat. It is moulded to form coverings suitable for steam-pipes and their fittings and sectional jackets for boilers and cylinders; it is furnished also in forms suitable for lining refrigerators, walls and roofs of buildings, fire-proof safes, etc. It was with a view of ascertaining the efficiency of this material as a non-conductor, or, rather, its relative efficiency among the various non-conducting materials in use, that the writer made the experiments about to be described. A block of magnesium carbonate or magnesia alba exhibits some interesting physical qualities. It is a smooth, white, close-grained solid, in outward appearance resembling a block of Paris plaster. It possesses the lightness of cork, the porosity of sponge, and withal a degree of firmness and strength that, in view of its levity, is quite remarkable. To examine more closely the properties of this substance, a number of 1-inch cubes were sawed from the commercial block-carbonate, also some bricks, that is, blocks measuring accurately 2 x 4 x 8 inches, the dimensions of an ordinary brick. The cubes weighed from 2.2 to 2.7 grammes, the bricks weighed 140 to 175 grammes (5 to 6 ounces). The bricks were carefully measured and weighed, and placed in vessels containing distilled water, in which they became gradually submerged, owing to the displacement by water of the air inclosed in the structure of the magnesium carbonate. After twenty-four hours the blocks were removed from the water, dried superficially by contact with filter-paper and weighed. From the increase in weight, the volume of the water absorbed, and consequently that of the air displaced by it, were obtained. For example: a block which when dry weighed 155

Jan 1, 1887

By S. Stutz

Coal, like most other minerals, only exceptionally occurs in a sufficiently pare state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more per cent. in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but moat frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypum. In both cases the impnrities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the manufacture of iron. Coke will coutain on an average at least fifty per cent. more ash and sulphur than the ram coal from which it is made. To the manufacturer of iron every additional per cent. of ash which his coal or coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight; that is, a certain part of tile coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the iron-master that coke containing lees ash makes the &lag or cinder more liquid and less incliner1 to stick to the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore arrd flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etd, from the coal has as yet only been successfully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By D. M. Davidson

THE drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of 110 ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered, and is drained by the Piney and Tye Rivers, which are tributary to the James. GEOLOGY The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 45° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelsonite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more promounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,1 the Ti02 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. SAMPLING METHODS AND PROCEDURE During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this possible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1946