Search Documents

By Henry G. Petrow, Edward S. Porter

MAJOR occurrences of lignite with significant uranium concentrations have been reported in western parts of the Dakotas, especially in Harding County, S.D., and Billings and Slope counties, N.D. Samples containing as much as 2 pct U3O8 were received at the Winchester Laboratory, but those deposits reportedly of major significance have generally contained 2 to 4 lb of uranium per ton of lignite. Most of the uranium appears to be associated with the carbon in the lignite as a urano-organic complex, although in most instances analysis of inorganic material has shown uranium values. Molybdenum is similarly associated with the carbon, and its concentrations generally parallel the uranium. The noncarboniferous material is mainly composed of gypsum, jarosite, bentonite, sandstone, and miscellaneous carbonates and silicates. The heating value of these lignites has been determined as about 3500 Btu on a dry lignite basis. The ash content of lignite has varied widely, the important samples containing 30 to 60 pct ash on a dry lignite basis. Because of the significant upgrading of uranium values obtained by ashing the lignite, and because recovery of uranium from raw lignite presented formidable processing problems, major emphasis at Winchester has been placed on devising methods to recover uranium from lignite calcines. Proper roasting removes the problem of organic fouling of solutions, reduces the size of the leaching plant for an equivalent uranium throughout, and generally provides equal or better acid leaching efficiency with less acid than can be obtained from the raw lignite.

Jan 9, 1957

By Frank L. Nason

In the year 1904 an eminent Swedish geologist prepared a report on the iron-ore reserves of the world. His estimates follow: Countries. Tons. United States,.1,100,000,000 Great Britain,.1,000,000,000 Germany,.2,200,000,000 Spain,.. 500,000,000 Russia and Finland,...... 1,500,000,000 France,..1,500,000,000 Sweden,..1,000,000,000 Austria-Hungary,....... 1,000,000,000 Other countries,1,200,000,000 Total,.10,000,000,000 The iron-ore allotted to the United States by the Swedish geologist is barely sufficient to last 20 years at. the present rate of consumption. On the other hand (according to Edwin C. Eckel,' from whom the above and following statistics are quoted), there is hardly need for worry on the part of our iron industries for the next two centuries or more. Upon the basis of careful work by the U. S. Geological Survey, in which Mr. Eckel has taken an important part, the following estimates are definitely, but by no means finally, given for the United States: District. Tons. Lake Superior District,... 1,500,000,000 to 2,000,000,000 f red hematite,.. 1,000,000,000 Alabama, brown hematite, hematite, . 725,000,000 red hematite,.. 200,000,000 Georgia, { brown hematite, . 125,000,000 Tennessee, { red hematite,.. 600,000,000 Tennessee, { brown hematite,hematite, . 225,000,000 f red hematite,.. 50,000,000 Virginia, } brown hematite, . 300,000,000 Total,..4,725,000,000 to 5,225,000,000

Jan 1, 1913

By James Norman

SPODUMENE is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content, it might be a desirable constituent of glass batches. The use of spodu-mene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components.1 The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manga-nese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li2O on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston, ? the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3 The methods described in the second publication' did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted.

Jan 1, 1940

By James Norman

SPODUMENE is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content it might be a desirable constituent of glass batches. The use of spodu-mene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components.1 The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manga-nese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li20 on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston, ? the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3 The methods described in the second publication' did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted.

Jan 1, 1940

By Harry Seltz

INTERMETALLIC compounds are formed in many binary metal systems. Some compounds are stable to their melting points, and others decompose at lower transition temperatures. Even those of the first class are dis-sociated in the liquid state, as indicated by the continuous for in of their solubility curves at their melting points1. While the lattice structures of some of these compounds have been determined, their thermodynamic properties have not been investigated. In this paper is described the determination of the free energy and heat of formation of the compound CdSb, which is of the first class mentioned above, melting congruently at 455° C. This compound shows a rhombic structure, and the lengths of the edges of the elementary cell containing four molecules are: a =6.52, b = 8.60, c = 4.16 A.2 There are three possible methods of determining the free energy of formation of a compound of this type. The first method, applying the third law of thermodynamics, requires the measurement of its heat capacity preferably to liquid hydrogen temperatures, and a calorimetric determination of its heat of formation. The second method involves the study of the equilibrium of the compound in some gas reaction, such as: CdSb + CO2 = CdO + CO + Sb From the known free energies of formation of CdO, CO2 and CO the free energy of formation of CdSb could be calculated. The third method measures the electromotive force of a galvanic cell in which the cell

Jan 1, 1935

By Leon Keller, William R. Van Slyke, James Stukel

Two 4-ft wide DSM screens were installed during 1957 in one unit of the two-unit heavy media cy- clone section of the Holman-Cliffs concentrator at Taconite, Minn., following successful laboratory test work on a 1-ft screen. The two screens materially reduced the amount of media sent to the magnetic separator cleaning circuit. Wear life was good and fine size capacity was high. Briefly, the Holman-Cliffs heavy media cyclone plant uses -65 mesh magnetite as media and 10-in. diam., 30º Ni-Hard cyclones as separatory vessels. Feed to the plant averages 130 long tons per hr of -1/8 in. +65 mesh material. The conventional heavy media circuit uses drum or spiral type separatory units and treats +l/8 or 3/16-in. material. The medium is generally -65 mesh ferrosilicon. Ore and media are readily separated by screening at about 6 mesh. At this size, capacity is high and wear and maintenance are not excessive. The heavy media cyclone plant requires an efficient separation between +65 mesh ore and -65 mesh media. To reduce costs, however, the separation was made at a coarser size with the result that the media was un- duly contaminated and it was necessary to clean large tonnages of media and ore in magnetic separators. Due to the high capital cost of these units, their number was kept to a minimum and, consequently, they were overloaded. As a result, the separation between magnetic media and nonmagnetics was not sharp and the magnetite losses were high.

Jan 10, 1958

By Haim Chiswik

IN recent years considerable attention has been devoted to the devel-opment of new commercial uses for silver, chiefly because of lowered prices and large stocks of the metal. This has led to increased interest in the phase diagrams of silver alloys. The silver-lead diagram is reported' to be of the simple eutectic type, but no measurements of the solubility of lead in silver have been made. The solubility of silver in lead has been estimated2 from diffusion experiments and resistance measurements to vary with temperature from 0.09 to 0.18 atomic per cent (0.05 to 0.10 weight per cent). Silver-rich silver-lead alloys have recently been recommended as high-strength bearing metals.3 The silver-bismuth diagram is similar.' The solubility of bismuth in silver has been estimated to be about 5.5 weight per cent on the basis of X-ray work.4 Matthiessen5 found a solubility of silver in bismuth from 0.25 to 0.50 per cent by conductivity measurements. Silver and thallium form the same type of diagram,1 with no data on their mutual miscibilities. We have studied the first two of these diagrams by X-ray methods, verifying their main features and determining the solubilities of lead and bismuth in silver at several temperatures. We also determined the solubility of thallium in silver at one temperature. The solubilities of silver in lead and in bismuth were found to be too low to be detectable.

Jan 1, 1940

By William Fink

THE investigation of aluminum alloy systems prior to 1923 was severely handicapped by the low purity of the best aluminum available. However, by that time, the electrolytic purification of aluminum had been developed by the Aluminum Company of America,(1)? and in May, 1923, there was initiated, under the direction of E. H. Dix, Jr.,(2) a program for the investigation of the aluminum-alloy systems using the purest electrolytically refined aluminum. Up to the present time 15 papers (a) have been published, most of which are on the binary aluminum systems. Work is now in progress on the ternary systems, and it seems probable that most of the future work will be on ternary systems. Therefore this survey of the binary aluminum systems investigated up to the present time (the sixteenth paper of the series) concludes the first phase of this program. Certain qualitative relations between corresponding portions of the various binary diagrams as well as between different parts of the same diagram were noted some time ago by R. S. Archer.(4) In the present . paper these relations and others are considered quantitatively by the application of well-known thermodynamic equations or by newly discovered empirical relations No attempt will be made here to present the history of the develop-ment of the thermodynamic equations defining equilibrium or their application to metallic systems, although a list of references is given at the end of this paper for those who are interested in this phase of the

Jan 1, 1934

By R. T. Mishler

Silver-gold. mine, in northern Mexico, with arrow veins in rhyolite. One fourth area developed has been ore. Deposits average 20 in. wide and 73 oz. silver per ton; diluted in mining to 40 oz. per ton. Developed by drifts and raises at 100-ft. intervals. Samples cut every 5 ft. Ore and waste sampled separately to make combined stoping width 3 or 3 1/2 ft. Ore reserves figured to sloping width; high assays not modified. Tonnage and assay of ore extracted higher than estimates. Ore stoped principally by cut and fill method. Cars from each stope counted and sampled. Cars check tonnage to concen¬trator within 1 per cent.; silver assay 9 per cent. high. Tonnage and assay from scopes corrected to agree with feed to concentrator. Profit or loss for each slope estimated monthly. THE Lucky-Tiger mine is a silver-gold property, situated at El Tigre, in the northeastern part of Sonora, Mexico, at, an elevation of 6000 ft. in the Sierra Madre Mountains. It is 30 miles by wagon road from the Esqueda station on the Nacozari railroad. Since its discovery in 1903, the mine has produced forty million ounces of silver. The ore has averaged 40 oz. silver and 0.25 oz. gold per ton. Copper, lead and zinc have been of minor importance, having averaged 0.4 per cent., 1.1 per cent., and 1.5 per cent., respectively. The richness of the ore,, combined with its occurrence in narrow veins, required the use of the more expensive methods of mining.

Jan 2, 1925

By B. B. Cox

The principal event during 1936 was the sale of Mosul Oilfields, Ltd. to Mosul Holdings, Ltd., a British company with French and American participation, and the expansion of its wildcat activities to untested structures on its West Tigris concession. Mosul Holdings continued the exploration of its low-gravity Qaiyarah-Najmah-Jawan-Qasab field. The Iraq Petroleum Company's systematic exploration and exploitation of its Kirkuk field was continued on a scientific unitized basis. Pressures and gas-oil ratios remained satisfactory. All wells were produced by flowing. A stabilization plant large enough to supply the 4,000,000-ton pipe line to the Mediterranean was completed at Kirkuk about the close of the year and only sweet oil is now being exported. The Khanaqin Oil Co., Ltd., a subsidiary of the Anglo-Iranian Oil Co., Ltd., continued the normal exploitation of its Naft Khaneh oil field, refining and marketing through the Rafidain Oil Co., Ltd. for local Iraq market. This field lies partly on the Iraq side of the boundary and partly on the Iranian side, the latter portion being known as Naft-i-Shah. Only the Iraq side is considered in this paper. Slightly more than 30,000,000 bbl. of crude was produced in Iraq during 1936. The I.P.C. exported all crude sold outside of Iraq and showed an increase of about 2,500,000 bbl. over the preceding year. Crude production in Iraq for export in 1934 was 7,096,669 bbl.'; in 1935 it was 27,014,904 bbl. and in 1936 it was 29,521,053 barrels.

Jan 1, 1937

By V. Runolinna, R. T. Hukki

Preliminary separation of precious metals by flotation can offer a simplification of the conventional method of treatment of anode slimes. Laboratory flotation experiments show that rich gold and silver concentrate can be obtained with excellent recoveries. THE purpose of this paper is to present the results of an investigation into the possibilities of separating precious metals from anode slimes by selective flotation. The work was carried out at the State Research Institute in Helsinki, Finland. The sample of anode slimes tested was submitted by the Outo-kumpu Co. in Finland. In 1947 the average assay of filtered and dried anode slimes in the Outokumpu refinery in Pori was as follows: Au, 0.50 pct; Ag, 9.38 pct; Cu, 11.02 pct; Ni, 45.21 pct; Pb, 2.62 pct; Fe, 0.60 pct; Sn, 1.00 pct; Sb, 0.04 pct; As, 0.70 pct; Se, 4.33 pct; S, 2.32 pct; SO,, 2.17 pct; SiO2, 2.25 pct. The daily assay naturally varies considerably from the figures presented above. The present conventional method of treatment of anode slimes consists of the steps shown in the flowsheet in fig. 1. As seen from this simplified flowsheet, the present method of treatment involves many steps by which the components of the anode slimes are removed one after another until the main products, gold and silver, may be separated. Due to the small scale of operations, the above procedure is carried out in small batches requiring considerable amount of manual labor. If, however, the anode slimes could be treated in

Jan 1, 1951

By V. Runolinna, R. T. Hukki

Preliminary separation of precious metals by flotation can offer a simplification of the conventional method of treatment of anode slimes. Laboratory flotation experiments show that rich gold and silver concentrate can be obtained with excellent recoveries. THE purpose of this paper is to present the results of an investigation into the possibilities of separating precious metals from anode slimes by selective flotation. The work was carried out at the State Research Institute in Helsinki, Finland. The sample of anode slimes tested was submitted by the Outo-kumpu Co. in Finland. In 1947 the average assay of filtered and dried anode slimes in the Outokumpu refinery in Pori was as follows: Au, 0.50 pct; Ag, 9.38 pct; Cu, 11.02 pct; Ni, 45.21 pct; Pb, 2.62 pct; Fe, 0.60 pct; Sn, 1.00 pct; Sb, 0.04 pct; As, 0.70 pct; Se, 4.33 pct; S, 2.32 pct; SO,, 2.17 pct; SiO2, 2.25 pct. The daily assay naturally varies considerably from the figures presented above. The present conventional method of treatment of anode slimes consists of the steps shown in the flowsheet in fig. 1. As seen from this simplified flowsheet, the present method of treatment involves many steps by which the components of the anode slimes are removed one after another until the main products, gold and silver, may be separated. Due to the small scale of operations, the above procedure is carried out in small batches requiring considerable amount of manual labor. If, however, the anode slimes could be treated in

Jan 1, 1951

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,' over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann' calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7'8 on the oxygen activities in these melts.

Jan 1, 1962

By Thomas H. Leggett

In speaking of the mining and economic conditions prevailing at the present time on the Rand, it is not my intention to go into the details of the mining practice, since this has been already well described both in the Transactions' and elsewhere,2 but rather to take a more comprehensive view of the industry and its surroundings as a whole, marking its general development and the lines of its future progress. In a paper entitled Deep-Level Shafts on the Witwaters-rand, with Remarks on a Method of Working the Greatest Number of Deep-Level Mines with the Fewest Possible Shafts,' presented to this Institute in August, 1900, I drew attention to the great cost of sinking the very deep vertical shafts that were then being seriously proposed as necessary for the development of the deeper areas, pointing out the strong advisability of working this ground by means of inclines to be sunk from the existing shafts of from 3,000 to 4,000 ft. in vertical depth. In this paper it is stated (p. 975): '" In short, practice upon the Rand now tends towards fewer vertical shafts and more underground inclines, especially for the very deep mining about to be undertaken." In consequence, the 6,000-ft. vertical shafts, at one time so much discuesed, have never been started, and they do not now seem likely ever to be. The necessity of placing all deep shafts further apart in order to make them control and exhaust larger areas was also dwelt upon. This economy wae vitally necessary for both

Jan 1, 1909

By V. F. Zackay, W. A. Goering

ALLOYS of iron and aluminum up to 35 wt pct aluminum are single-phase solid solutions, and are of potentially wide applicability.1-3 In spite of early and continued interest1-4 little progress has been made until recently in the preparation and evaluation of sound alloys containing more than 6 wt pct aluminum. Vacuum-melting techniques for the production of ductile Fe-A1 alloys have been described recently.1-7 A. procedure for air melting these alloys is presented here. Low-carbon iron is induction melted without a slag in a rammed magnesia crucible. At the beginning of melt-down, aluminum pig (99.95 pct Al), charged in a clay-graphite bottom-pouring crucible is placed in a pot furnace at 1800°F. The primary deoxidation of the molten iron after melt-down is effected by the addition of 0.1 pct aluminum and 0.5 pct manganese. (Hilty and Crafts" have reported a significant increase in the deoxidation efficiency of the aluminum and manganese combination over that of the aluminum alone.) A more drastic deoxidation designed to reduce the oxyen content to the lowest possible level is accomplished by plunging metallic calcium to the bottom of the melt. This is done by wiring small cubes of the metal to a steel rod. A circular shield larger than the diameter of the crucible opening is attached to the rod so that any spa'ttering of the molten metal will not endanger the operator. Since the temperature of the molten metal is above the boiling point of calcium, the bath is vigclrously purged by calcium vapor. It is believed that the calcium-vapor treatment permits a homogeneous distribution of calcium in the melt. Owing to the vigor of the reaction the temperature of the molten metal should be kept below 2900°F prior to the calcium addition. A total of 0.05 pct calcium is added in two stages in this manner. The second calcium deoxidation is made just before charging the molten aluminum into the iron, in order that an excess of calcium be present for the remainder of the melt. The aluminum, which has been removed from the holding furnace, is then hydrogen degassed by bubbling chlorine through a quartz tube immersed in the molten aluminum. The hydrogen-chlorine reaction is an exothermic one preventing the solidification of the aluminum during the 5-min chlorination. Approximately 0.1 pct calcium, based on the amount of aluminum, is then added to the aluminum. A further excess of calcium is introduced into the melt in this manner. The oxide dross is removed, fluorspar is added to the molten iron, and the molten aluminum is poured through the fluorspar slag. The fluorspar should be dried thoroughly prior to its use, as any water present will react with the aluminum. Aluminum oxide formed during the pouring operation reacts with the fluorspar slag to form gaseous aluminum fluoride and calcium oxide. A forced-draft ventilating system is required for this operation as aluminum fluoride is toxic. As soon as the molten aluminum has been added, vigorous manual stirring of the melt is required because the slag-aluminum oxide reaction is highly exothermic and tends to take place near the top of the melt. The combination of high temperature and the slagging action of the fluorspar quickly erodes the crucible at the slag line if the aluminum is not stirred uniformly into the melt. It has been found that at least 4 min of manual stirring combined with induction stirring are necessary to ensure homogeneity. The power is shut off 1 min prior to pouring to allow metal and slag to separate. As much slag as possible is removed from the melt, which is then poured directly into cast-iron molds. A mold wash of aluminum oxide is used to prevent ingot sticking. For slab ingots which are to be rolled into sheet, a carbon-tetrachloride vapor atmosphere or a chlorinated-pitch mold wash is desirable, as the aluminum oxide formed in the pouring operation is subsequently removed by the chlorine in the presence of carbon." As in vacuum melting, a pouring temperature of about 2900°F is recommended. Adequate hot-topping is important as iron-aluminum ingots are subject to very deep piping. Ingots are removed from the molds and buried in vermiculite, where they are allowed to cool slowly to room temperature. The ingots are radiographed,

Jan 1, 1959

By M. C. Flemings, G. E. Nereo

General expressions are given to describe macro-segregation in castings and ingots which results from mass flow of solute-rich liquid to feed solidification and thermal contractions. Analytical solutions are given for solidification with planar isotherms (unidirectional and bidirectional heat flow). These solutions describe inverse segregation and centerline segregation. Numerical examples are given for A1-4.5 pct Cu alloy. In 1540, Vannoccio Biringuccio published one of the first references to macrosegregation, describing the problem of exudation and inverse segregation in the manufacture of bronze gun barrels.' Since then, a great many studies of macrosegregation have been reported. Recent work of particular engineering interest includes that of Marburg 2 and others:" on centerline segregation and other types of segregation in large steel ingots, and work of Adams,5 Scheil, 6 and Kirkaldy and youdelis7 on inverse segregation in nonferrous ingots. In most studies on this subject, the various types of macrosegregation have been treated as separate phenomena. For example, quite different mechanisms have been proposed for formation of centerline segregation, negative cone of segregation, inverse segregation, banding, and so forth. In this, and in several papers to follow, it is proposed that these as well as other types of macrosegregation result from the same basic mechanism and can be quantitatively described by the same basic equation. It has often been suggested that some types of segregation (such as centerline segregation and banding) occur as a result of buildup of solute at the tips of growing dendrites.2-4 ,8-10 As example, banding can be induced in centrifugal castings by mechanical vibration, and Northcott 10 suggests this might be due to the influence of the vibration on the boundary layer at the dendrite tips of the growing dendrites. However, in view of the extremely small boundary layer known to exist at the tips of the dendrites,11,12 any interpretation of macrosegregation based on this boundary layer is clearly incorrect. Note that experiment has shown that significant buildup of solute does not occur at dendrite tips in ingot solidification, but even if such buildup occurred the thickness of the enriched zone would only be the order of D/U where D is liquid diffusion coefficient and U is dendrite tip velocity. For usual casting or ingot solidification this solute-enriched layer is 10"3 cm, far too small to account, for example, for centerline segregation.11'12 It has also been suggested that convection in the bulk liquid (ahead of the advancing dendrites) might cause segregation by sweeping away the solute-rich boundary layer in front of the dendrites.3 However, since there is no significant boundary layer, this explanation must be incorrect. The convection might directly cause segregation by penetrating between the dendrite arms, and presumably in a rimming steel ingot it is sufficiently vigorous to cause some segregation in this way. Centerline segregation, however, cannot be interpreted as resulting from this convection since a sharply segregated zone is usually found near the centerline, with the bulk of the ingot being nearly of nominal composition. If convection in the bulk liquid were the direct cause, a gradual change in ingot composition over the entire cross section would be expected. It is known that sudden changes in convection of the bulk liquid during solidification can result in banding,14 but it is not clear that the banding results directly from the effect of convection on solute distribution. Changes in convection also affect thermal conditions in the liquid-solid region of a solidifying ingot. It will be seen later in this paper, and in a paper to follow, that macrosegregation is strongly influenced by these thermal changes. Recognizing that in some cases of ingot solidification (as in solidification of rimming steels) convection in the bulk liquid may have a direct effect on solute distribution, we neglect it in this paper and in the several to follow. We then derive general expressions describing macrosegregation which results from the mechanism of interdendritic flow of solute-rich liquid

Jan 1, 1968

By Carl F. Lutz, Robert F. Mehl

A layer of brass was formed on 0 brass using a vapor-solid reaction technique. The variation in composition with distance within the phase layer and across the a -ß interface was determined by an electron probe. The diffusivities were calculated as a function of concentration; the diffusion coefficient in brass was found to change by a factor of twenty-five over a compositional range of 8 at. pct. An explanation is proposed to account for the large change in the diffusivity, based on possible stresses in the diffusion zone; it is suggested that the concentration dependence of the thermodynamic factor might decrease the activation energy with increasing zinc content. ALTHOUGH the body of data on diffusion coefficients (D- values) in terminal solid solutions and in isomorphous systems is quite large, there is but little quantitative information for intermediate alloy phases. This paper recounts measurements of D-values for the ? phase in the Cu-Zn system. The experimental method employed consists in the forming of alloy layers and determining and analyzing the concentration-distance (c-x) curve. The experimental method employed could have been applied to several systems; the Cu-Zn system was chosen because the D-values in the a and ß phases are well known, and can thus be used for purposes of comparison. The rates of growth, of intermediate alloy layers are known for a number of systems. In nearly all cases the thickness varies parabolically with time, as to be expected if the rate of growth is controlled by the D-values. In a few cases, nonparabolic behavior has been noted.1 Nonparabolic growth may be the result of a) a variation of the composition at the phase interface with time, b) interface-controlled kinetics, c) short diffusion times coupled with long vacancy lifetimes (in vacancy diffusion),2 and d) crystal reorientation during diffusion in anisotropic systems.3 In the Al-Ni system4 and in the Al-u5 system parabolic growth kinetics are slowly approached after an initial transient period. In general those phases stable at a given temperature in a system A-B appear as separate phase layers when A and B are put in contact and given a diffusion he at-treatment. In most cases the compositions at the interface of adjacent phase layers are those read from the phase diagrams for the termini of the respective phases. This discontinuity in concentration is taken as independent of time, and the growth of one phase at the expense of another is assumed to be independent of interface kinetics, i.e., the rate of interface movement is controlled by volume diffusion in the phases concerned. wagner6 has given many solutions for multi-phase diffusion processes, assuming that the chemical diffusion coefficient, D, is independent of concentration, as have others. Jost7 has pointed out that the familiar Boltzmann-Matano solution is as valid for a (c-x) curve exhibiting concentration discontinuities at phase boundaries as for the usual single-phase case. Heumann and associates8,9 have applied this solution to the multi-phase case, but lacking concentration data within the several layers were forced to assume linear concentration gradients, thus calculating only average D-values. The purposes of the present study were: 1) to determine the dependence of D on concentration, 2) to calculate the intrinsic diffusion coefficients D?Cu and D?Zn, 3) to establish the time-law for the movement of the interface, 4) to determine the concentration limits at the ß-? interface, and, 5) to attempt to clarify the mechanism of diffusion. EXPERIMENTAL PROCEDURE The ? phase is exceedingly brittle; conventional solid couples and conventional sectioning methods were thus inapplicable. Vapor-solid couples were accordingly employed. Unfortunately the equilibrium vapor pressures of Zn for the ? phase are unknown; to escape this awkwardness, samples were enclosed in a capsule containing powder of an alloy of known composition, sufficiently large in quantity as to be effectively an infinite source, maintaining the concentration of Zn at the sample surface constant with time. The sources of Zn-vapor which can be employed in reaction with Cu, or a brass, or ß brass, to form a layer of ? brass satisfactorily wide in concentration range, are alloys of the phases ?, or ? + E or ? + d (depending on the temperature).

Jan 1, 1962

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By R. H. McLean

Jet impingement produces two mechanisms to clean the bottom of a borehole during jet-bit drilling operations. One is an impact-pressure wave in the immediate area of jet impingement. The other is crossflow, which spreads across the bottom away from the pressure wave. Measurements of the vertical distribution of the cross-flow at several positions beneath a 4 3/4-in. tricone jet bit in a laboratory model show that the maximum velocity in the crossflow is directly proportional to the square root of the product of the rate of flow and the velocity of the jets through the nozzles (QV). Other measurements in the laboratory model show that gradients in the impact-pressure wave are directly proportional to the jet QV if the diameters of the nozzles are held constant. Consistency of the basic relationships through changes in the Reynolds numbers of the jets from 31,000 to 93,000 suggests that the laboratory results should be representative of typical flow in field operations having higher Reynolds numbers. Estimates of the impact-pressure waves under conditions other than those in the jet-bit model may be made by comparison with a less complex model—impingement of a jet against an unrestricted flat surface normal to the jet. Equations derived from current jet technology describe the wave in this simple system for a wide range of conditions. INTRODUCTION The efficiency of rotary drilling operations is strongly linked to the efficiency with which cuttings are removed. Cuttings remaining on the bottom of the borehole will impede further penetration by the bit until they are removed. Wasteful regrinding is prevented if the fluid circulated past the bit removes cuttings as rapidly as they are made. Most investigations of bottom-hole cleaning under bits have been concerned with the rate-of-penetration effects of bit type, nozzle configuration, fluid properties, pressure gradients and utilization of hydraulic horsepower. These investigations have shown that drilling muds, weighted to keep the pressure in the borehole greater than in adjacent formations and carrying material which forms a filter cake, apparently plaster cuttings against the bottom, making them difficult to remove. In addition to a demonstration of the factors causing poor cleaning, the most significant result of these previous investigations has been the increased use of jet bits accompanied by better hydraulic programs and better selection of drilling fluids. Undoubtedly, these practices have improved bottom-hole cleaning, but rates of penetration when drilling with muds are still often lower than would be expected with perfect cleaning." Although there is general agreement with the concept that increasing hydraulic energy at a jet bit often increases the rate of penetration by improving cleaning, research workers have differed as to the best criterion for evalyating hydraulics. Some lean toward maximizing the product of the rate of flow and the velocity through the nozzles (QV) others prefer to maximize the hydraulic horsepower at the bit;'"-' "till another says that neither criterion is universally suitable."' This controversy shows that conclusive field evidence has not established the superiority of either of these criteria. Analysis of the fluid flow which cleans the bottom should contribute to resolving the controversy. Impinging jets clean the bottom by creating two mechanisms capable of dislodging cuttings. One is the impact from the momentum of the jet and the other is the flaw parallel to the bottom away from the area of impingement. The impact force appears in the form of a pressure wave on the bottom and, in this paper, is called the impact-pressure wave. The flow parallel to the bottom is called crossflow. Fig. 1 illustrates these two mechanisms. This paper describes crossflow and the impact-pressure wave beneath jet bits and relates them to controllable parameters. Through these relations, criteria for use in designing hydraulics to achieve maximum use of the mechanisms of cleaning are derived. PROPERTIES OF CROSSFLOW CONCEPTS DEVELOPED IN PREVIOUS INVESTIGATIONS Concepts of scavenging the bottom by crossflow have been well discussed by Bobo, et al." They examine the means by which crossflow may create forces on cuttings and conclude that the cleaning action of crossflow can be increased by increasing the velocity of the flow stream close to the bottom. Using boundary layer theory, they indicate that a reduction in the viscosity of the drilling

Jan 1, 1965

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964