Search Documents

By T. Kilner, A. Plumtree

DURING an investigation of electro-deposited silver structures, samples were prepared for metallographic examination by cold mounting in plastic, grinding on successive grades of emery paper down to 3/0, and chemically polishing by swabbing using the chromic acid solution described by Gilpin and Worzala.1 Attempts to etch these samples using the standard solutions described for silver (e.g., 5 pet KCN-5 pet Na2S2O8, H2O2-NH4OH, and various potassium dichro-mate solutions) all failed to give good results due to staining of the samples and to rapid etching. The staining was caused by the chromic acid polishing solution being trapped in small fissures between the sample and the mounting plastic, and also in small fissures in the sample itself. To overcome these difficulties, an etchant was developed which prevented staining at the same time as it slowly etched the sample. This resulted in a very clean, crisply etched surface as shown in Figs. 1 and 2. This etch consisted of 10 ml of orthophosphoric acid, 10 ml of distilled water, and 2 drops of the polishing solution noted above,' which is made by mixing 100 ml of saturated CrO3 solution, 45 ml of 10 pet HC1 solution, and 800 ml of distilled water. The etching procedure involved taking the final polished sample, either immersing or swabbing in the etchant for a period of 1 to 2 min, rinsing as quickly as possible in distilled water, alcohol, and ethyl ether in that order, and then immediately drying. This etch is easily controlled due to its slow rate of etching, and produces samples with clean, sharp surfaces. Pits due to overetching produced varying contrast effects when viewed under polarized light, and are therefore obviously useful for revealing many structural details within the sample. Another effect of overetching was to produce a height varia-

Jan 1, 1968

By AIME AIME

Annual net production of crude oil from the Anglo-Iranian, Oil Company's fields in Iran for the years 1940 through 1945 amounted to: YEAR TOTAL PRODUCTION (Long Tons) 1940 8,626,639 1941 6,605,320 1942 9,399,231 1943 9,705,769 1944 13,274,243 1945 16,835,000 (preliminary figure) All developed fields were on almost continuous production throughout the war, though their operation naturally was hampered by war conditions, which affected particularly supplies of equipment.

Jan 1, 1946

By Frederick C. Hull, Robert F. Mehl, Robert A. Colton

IT is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth 12 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in 1939 3 Two types of process were described (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures, and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth Both cases are met in the formation of pearlite from austenite (Fig 1),2,3 the former, occurring near the knee of the S-curve has been named "grain-boundary transformation," and the latter, occurring at temperatures near AeI, has been named "group-nodule transformation " In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important''' to obtain data on the rate of nucleation and the rate of growth of pearlite Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the actors that affect hardenability, when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite 2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature,, and the degree of homogeneity of the parent austenite The studies are restricted chiefly to plain carbon commercial steels PREVIOUS DATA ON RAID OF NUCLEATION AND RATE OF GROWTH Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Mehl,1 and by Dorn, De Garmo and Flanigan22 It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc ), austenite grain size, and mode of formation of pearlite at the temperatures given

Jan 1, 1942

By R. L. Tobie

Handling and storing ore at transfer points underground are encountered frequently. An ideal solution to these troubles is probably still to be found, but at the Mather mine "B" shaft a method incorporating scraping trenches has been developed giving better service, from the standpoint of safety and simplicity, than obtained from other schemes. When shaft pockets are used for storage, the size of the ground opening required to assure capacity is often prohibitive, and shaft depth below the last level can become excessive, particularly if a crushing station is used. Also, if the material being handled contains large amounts of wet fines, it is difficult, if not impossible, to hold the material with regular chute gates. In order to remedy these problems Cleveland-Cliffs' Mather "B" has utilized three types of trenches. Types I and I1 are now in service and the third is under construction.

Jan 4, 1955

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By H. R. Ogden

The notch sensitivity of titanium alloys is affected by impurity content, microstructure, and heat treatment. Using notch tensile properties to evaluate notch sensitivity, three commercial titanium-base alloys were investigated over the temperature range of -320o to 390°F. The alloys studied were Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo. Six interstitial levels were studied for each alloy in four mi-crostmctural conditions. The ff- 0 alloys were studied in both the annealed and heat-treated condition. All tests were conducted using 1/4-in. diam round tensile samples. The notched samples had a 50 pct notch with a notch sharpness (a/r) of 53, corresponding to Kt 6.3. Notch sensitivity was increased by increased interstitial content, low temperature, and acicular-type microstructures. The heat-treated, high-interstitial content - 13 alloys were more notch sensitive than the same alloys in the annealed condition. In addition, minima in the notch tensile-temperature curves were observed at temperatures near 32°F. These minima became more pronounced with increasing interstitial content. 1 HE increaseduse of titanium alloys in high strength applications at subzero temperatures requires that a better under standing of the low-temperature behavior of the alloys be obtained. At low temperatures, metals generally exhibit increased strength with lowered ductility and tohness. Notch sensitivity and the factors which influence it become more important as the strength level is increased and the temperature is decreased. Some of the factor s which affect notch sensitivity in ti- tanium alloys are composition, interstitial content, microstructure, and heat-treatment condition. In this paper, the results of a study of these variables on the notch sensitivity of three titanium alloys at temperatures from —320o to 390o are reported. The notch geometry selected for this program was chosen to provide a severe test of notch sensitivity. The ability of the metal to flow without initiating fracture under these severe conditions is reflected in the notch-strength values. Since notch strength is, in part, determined by the constraint exerted by the combined tensile stresses, the behavior of notch specimens reflects the properties of the material under combined stresses. For example, a material with a high notch-unnotch strength ratio may be expected to withstand the biaxial stresses encountered in a pressure vessel better than a material with a low ratio of notch-unnotch strengths. This implies that maximum strength alone is not a sufficient criterion for applications of this type. It further may be concluded that the various conditions that promote poor notch behavior also will affect adversely the performance of materials under combined stresses. In the alloys studied, these included low temperatures, high interstitial levels, and hasformed microstructures. EXPERIMENTAL PROCEDURES Three alloys, Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo, were purchased from commercial producers as 2-in.-dam rod stock. Oxygen and nitrogen were added to these alloys by remelting to obtain a variety of interstitial contents as shown in Table I. In order to Compensate for the much more potent strengthening effect of nitrogen compared with oxygen, an oxygen equivalent content is used to describe the total oxygen plus nitrogen contents studied. It has been suggested previously1 thatnitro-gen is approximately twice as effective in strengthening as oxygen, and carbon, to the extent it is in so-

Jan 1, 1962

Jan 1, 1925

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By C. P. Gazzara and

The modulus of elasticity and yield strength of commercially pure, annealed titanium sheet was investigated at room temperature as a function of strain rate and direction of loading. The value of E varied with direction of measuremeni in the sheet but was unaffected by strain rate in the range 0.04 x 10-to 10-2min-1. The yield strength increased with increase it2 strain rate and varied with specimen orientation. VALUES of the modulus of elasticity, E, in tension for commercially pure titanium have been reported at from 14 to 20Xl06 psi.&apos; Reasons suggested for this variation have been a) composition, b) strain rate, c) texturing, and d) creep. For example, alloys of titanium with aluminum, manganese, and nitrogen have yielded modulus values of from 12.5 to 16.8 x lo6 psi at room temperature.&apos; It was shown by Klier that the modulus in titanium plate was sensi-tive to strain rate. while Dotson and kattus meas- ured variations in E as the strain rate was increased from 3X to 60 min-l. For RC-7OA, 0.040-in. titanium sheet at room temperature Dotson and Kattus found that the average values of E, for specimens in the rolling direction, increased from 14.7 to 16.0 X lo6 psi as the strain rate increased. Simultaneously, the 0.2 pct yield strength increased from 74,700 to 95,700 psi for the same specimens. Differences in yield strength and E have been reported as a function of directionality in titanium sheet.= Dotson and Kattus report such an effect, and Feola6 found in annealed titanium sheet marked anisotropy in tensile strength, yield strength, reduction in area and elongation at room temperature, with

Jan 1, 1961

By H. O. Hofman

WITH the exception of lead sulphate, all common metallic sulphates are completely decomposed upon heating into metallic oxide, sulphur trioxide, sulphur dioxide and oxygen. Some give up their trioxide readily at a low temperature, others require considerable heat and much time to be completely freed from sulphur. Kerl in 1881 arranged the principal metallic sulphates as they are decomposed by a rising temperature in the following order: silver, iron, copper, zinc, nickel, cobalt, manganese and lead, lead sulphate being decomposed only slightly at a white heat. The researches of Bradford, published in 1903, show, however, that ferrous sulphate is decom¬posed at 590° C., cupric sulphate at G53° C. and argentic sulphate at 1,095° C. By the present investigation it will be seen that zinc sulphate is decomposed at 739° C. As far then as our present knowledge goes, the order in which the decomposition of the leading metallic sulphates takes place is the one given in Table I.

Jan 1, 1905

By S. K. Kawatra

The paper describes a system for on-line analysis of ash in solids in coal slurries for coal cleaning operations. The system consists of two sensors: 1) gama density gauge, and 2) ash sensor. The operational characteristics of each sensor are discussed.

Jan 1, 1980

By M. E. Nicholson

IT has been suggested by a number of investigators, I including Hume-Rothery and Raynor,&apos; that certain intermediate phases in metal systems take on interstitial crystal structures because of an appropriate ratio of radii of the two atoms. If the size factor is an important parameter in determining whether or not an intermediate phase will have an interstitial structure, then it would appear reasonable that the relative sizes of interstitial atoms should have a direct relation to their solubilities in interstitial compounds. It was on such a basis that Petch,&apos; in his discussion of the cementite structure, concluded that nitrogen is the only possible element which could replace carbon. Recent X-ray studies by Jacka indicate that the solid solubility of nitrogen in cementite is negligible. If this is the case, then on the basis of size factor it would not be expected that any element can replace carbon in FeaC, since according to Schwarzkopf and Kieffer4 the covalent atomic radii of nitrogen, carbon, and boron are 0.71, 0.76, and 0.87A, respectively. Nevertheless, Vogel and Tammann in 1922 indicated that a quasi-binary relation exists between the interstitial compounds FeaC and Fe2B and that the solid solubility of boron in FeaC at approximately 1150°C is 1.4 pct B by weight. Because of the apparent disagreement between theory and experiment, the solid solubility of boron in FeaC has been reinvestigated. In addition, the influence of boron on the saturation magnetic moment (per gram) and Curie temperature of cementite was determined. Experimental Procedure A series of Fe-B-C alloys which varied in boron content from 0 to 5.4 wt pct B were prepared by arc melting a 50-g ingot using carbonyl iron, Ache-son AUC graphite, and Cooper grade A boron for starting materials. The composition of these alloys is listed in Table I and shown graphically in Fig. 1. The samples represented by the solid circles were used for X-ray analysis and Curie temperature measurements; by the squares, samples used for quantitative metallography; and by the triangles, samples used for saturation magnetic moment measurements and Curie temperature measurements. After arc melting and subsequent quenching from 1000°C, so that all phases in the resulting microstructure were brittle, one half of the 50-g ingots were pulverized until a powder was obtained which was less than 100 mesh. These powders were then homogenized in evacuated Vycor capsules at 1000°C for 24 hr and water quenched. Although the homogenized powder had sintered somewhat, it was suitable for saturation magnetic moment and Curie temperature determinations, for which the 60 to 100-mesh fraction of the powder was used. For X-ray analysis the homogenized powder was crushed again until a 300-mesh powder was obtained. After crushing, the powder was mixed with Alundum of approximately the same grit size to prevent sinter-

Jan 1, 1958

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite&apos;" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By Hans W. Schreiber, David W. Neuhaus

INTRODUCTION The Sunshine Mining Company&apos;s 16-to-1 silver deposit and mine project are located 384 kilometers (240 miles) southeast of Reno and 360 kilometers (225 miles northwest of Las Vegas, near Silver Peak in Esmeralda County, Nevada, at an elevation of about 2,300 meters (7,000 feet). The deposit was being developed, in 1980, with an anticipated mining and milling rate of 150,000 tons per year (500 tons per day). Mining is by underground, blast-hole open stoping with rubber-tire haul-age out of the mine to a straight cyanide plant about 5.5 kilometers (3.5 miles) from the mine. The product is a gold-silver dore which may be further refined at Sunshine&apos;s new refinery in Kellogg, Idaho. The cash required for investment was obtained through the sale of $25 million worth of 6 l/2h silver-indexed bonds. Some $15.0 million were directed toward development of the 16-to-1 Mine. These bonds, which were underwritten by Drexel Burnham Lambert of Chicago in April of 1980, are redeemable on or after April 15, 1985 or payable at maturity on April 15, 1995 at the greater of either $1,000 or the market price of 50 ounces of silver. Behre Dolbear acknowledges the kindness of the Sunshine Mining Company (Sunshine) for allowing the presentation of the subject material for this Case Study. APPLICABILITY AS CASE STUDY Reasons for Choosing 16-to-1 The reasons for choosing the 16-to-1 Mine as a case study follow: 1. The project is simple and compact. 2. The mine is small -- thus relevant to other contemplated precious metal operaions in the western states. 3. The areas of risk are readily identifiable. 4. A change to project financing was under consideration. 5. A substantial decline in the price of silver was experienced during development. 6. Behre Dolbear undertook one of the first feasibility studies of The 16-to-1 and thus has some familiarity with the project. Historical Summary The following history serves as a setting: 1. Late 1920s -- minor "production"(?) via shallow pitting. 2. Mid-1930s -- neighboring Nivlok Mine successfully put into production. 3. Late 1950s (?) -- Callahan Mining Company acquired rights and drilled -- results inconclusive; Callahan turned property back to Arthur Baker, who had originally interested Callahan in 16-to-1 on the basis of its similarity with Nivlok Mine.

Jan 1, 1985

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.&apos;-&apos; Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.&apos; There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the &apos;&apos;vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By A. A. Collins

H. R. BIANCO*—I should like to ask Mr. Collins if that statement he made about the addition of drosses to the blast furnace slowing down the blast furnace is a result of his own experience or a result of the experience of some older metallurgists; and perhaps I should ask him to define the type of drosses that he means. A. A. COLLINS (author&apos;s reply)— That has been my own personal experience with dross. On various occasions at Chihuahua we attempted to incorporate the dross in our regular blast furnace charge and to shut down the dross re-verberatory to try to save some money. As expected, we had very poor results. I think that Ed Fleming will well remember on one occasion, that was back about 1933, when we attempted the first experiment along this line, and as a result of the sulphur addition to the blast furnace to matte out the copper we ended up with hanging furnaces and mushy slags and abandoned the dross experiment, once again turning to the use of the reverbera-tory for handling dross. H. R. BIANCO—Is that dross you refer to from the drossing kettle ? A. A. COLLINS—Yes, the dross that I am referring to came from drossing kettles. Furthermore, to back up my previous assertion, I had occasion in 1943, while up at Leadville, to once again experience the routing of dross through the blast furnace with its sulphur addition, since they had no dross re-verberatory, and to observe that once thf dross was removed, the furnace was speeded up almost 100 tons a day. All of these are personal experiences and I think that Mr. Feddersen also has had a little experience along this line —in fact, I believe all of us have had some experience. H. R. BIANCO—I know at Trail they recirculate considerable dross through the blast furnaces and we also recirculate dross at Herculaneuin and I am not aware that it has done much towards slowing down the blast furnace. A. A. COLLINS—We have always had very poor results. In the first place you have got to add a sulphur addition to pick up that copper and once you do that, that sulphur is apt to combine with some of the zinc and you are going to form a little mush; before you know it you have furnace hangs and a poor working furnace. Now of course that depends on the amount of zinc you have on charge. But in 1943, Leadville had roughly about 7 pet zinc in their slag and it worked very poorly. Previously when they had 4 or 5 pet zinc in their slag it did not matter. B. L. SACKETT* At Tooele we had a great deal of experience with copper. We have always been able to keep a lead well, however, in spite of the fact we have run as much as 5 pet copper and only 15 pet lead on the charge. But regarding the handling of dross, our dross reverberatory furnace is only 7 or 8 years old. Before that we recirculated the dross through the furnace and thought we were doing a pretty nice job. Of course these things are all more or less relative—in other words you establish a certain condition much better than one of a few years ago and possibly as good as any other of which you know and you think you have pretty good results. When we first took the dross off of the blast furnace and put it through the dross reverberatory furnace we immediately found out that we had gained something very real in furnace speed. Since that time there have been occasions when, because of the dross reverberatory being down, we have had to use dross again through the blast furnace and that has checked our original experience in slowing down the furnace very definitely. So we feel that a dross reverberatory is a very valuable asset at the Tooele Plant. A. A. CENTER*—Mr. Sackett&apos;s being here reminds me of trying to run with a minimum of lead concentrates the maximum of dross producing electrolytic zinc plant residue. He came up from International Smelting Co. to help us get started on that. We took an old copper blast furnace at Great Falls, Montana, and made a lead furnace out of it by putting a lead well on the other long side which of course is a very unorthodox lead blast furnace. Our aim was to treat the residue from the electrolytic zinc plant, as I said, with a minimum of lead concentrates. That meant a maximum amount of dross. At that time selective flotation was not general practice, so our zinc concentrates ran relatively high in copper and other dross-producing elements; and of course these were largely in the zinc plant residue. I think we might call it muscle metallurgy, but we had an interesting, successful experience there and we ran for over a year thanks to Mr. Sackett&apos;s helping us get started. I have the details, but time does not permit. We did well enough so that the A. S. and R. Co. at East Helena kept boosting up the offer to us for the electrolytic zinc plant residue and there was not enough lead concentrate to supply two lead smelters there in Montana, so the matter finally finished up by the A. S. and R. Co. taking all of the residue under long term contracts.

Jan 1, 1950

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was (&apos;Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350&apos; to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.&apos; Fig I shows a log D vs. log t plot of French&apos;s data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French&apos;s data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.&apos; Walker&apos;s specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker&apos;s data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By John Towers, Paul A. Beck, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350&apos; to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.&apos; Fig I shows a log D vs. log t plot of French&apos;s data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French&apos;s data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.&apos; Walker&apos;s specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker&apos;s data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949