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By Arnold K. Reese

It is not the purpose of the writer to set forth in these notes anything new or surprising in blast-furnace practice, but simply to lay before the Institute the somewhat unusual results obtained during a period of six consecutive months, ending April 30, 1896, at the Dover furnace of the Penn Iron and Coal Co., and to give, with these results, the conditions under which they were obtained, and all figures pertaining to that period. This plant was entirely rebuilt, on thoroughly modern and improved plans, in the spring of 1895, by Frank C. Roberts & Co., of Philadelphia.

Jan 1, 1898

By R. P. Agarwala, M. S. Anand, S. P. Murarka

Using the residual radioactivity technique, grain boundary diffusion of chromium in the a phase and lattice diffusion in the a and the ß phases of zirconiuttz have heen studied. The diffusivities (in units of square centiwzeters per second) have heen expressed as THE rate of diffusion of atoms along surfaces and grain boundaries is much greater than that through the bulk of metals. These processes dominate over volume diffusion at lower temperatures and can be isolated from it by virtue of the fact they yield high diffusion coefficients and low activation energies. In zirconium, however, it has been difficult to identify the volume-diffusion parameters separately. The values of diffusivities in a and ß phases yield activation energies which are much lower than those for volume diffusion calculated from semiempirical or empirical relations.1-3 Diffusion frequencies (Do) are also low, especially in the a phase, and they yield negative entropies of activation.4 Similar results have been obtained for the diffusion studies in titanium.5 It is yet to be investigated whether in these cases diffusion is controlled by some extraneous factor like high reactivity of these metals, or some different mechanism is operative as suggested by Pound et a1.6 However, Federer and Lundy,7 in a recent study of the diffusion of zir-conium-95 and columbium-95 in zirconium, and Gibbs et al.,8 in the study of impurity diffusion in titanium, found a temperature dependence of D, Do, and Q. Their study yielded low values of Do and Q at low temperatures, as has been found by other workers, and fairly high values at high tempera-

Jan 1, 1965

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By Edward I. Salkovitz

THE determination of the orientation of metal single crystals and the studies of plastic deformation are greatly facilitated by the use of the stereographic projection. To draw a standard projection of the crystal it is necessary to have a tabulation of the angles between the various crystal-lographic planes of the particular crystal studied. Bozorth' has published such a table for the cubic system which can be found in many reference books; such convenient tabulation for the hexagonal metals, however, does not appear to be in the literature, although scores of workers have calculated these angles. Therefore, Table I of angles for magnesium, zinc, and cadmium has been compiled. Since the c/a ratio is different for each of these metals, three separate calculations are necessary. The angles 4 between (HKIL) and (hkil) were calculated by means of the formula: Hh+Kk+½(Hk + hK)1+~3aLl cos The c/a ratios were calculated from data given in the 1948 edition of Metals Handbook. Fig. 1 is a typical (0001) standard projection of zinc. For all practical purposes, it serves for cadmium as well, as can be seen from the table. For magnesium, however, it is necessary to construct another net. R. M. Bozorth: Physical Review. (1925) 26, 390.

Jan 1, 1952

By Walter W. Bradley

(Three, papers included, in this discussion are classified as Mining Geology and also as one of the following-A, Metal Mining: B, Milling and Concentration: L, Geophysics. These papers are TP 2255, TP 2092 and TP 2038.) CONTENTS [PAGE Review of Fluorescence as Applied to Minerals, with Special Reference to Scheelite. (TP 1967 by J. W. VANDERWILT, Min. Tech., March 1946. Discussion by WALTER W. BRADLEY) I Geologic Interpretation of Magnetic Exploration on the Mesabi Range, Minnesota. (TP 2038 by R. B. H. JONES, Min. Tech., July 1946. Discussion by ROBERT B. SOSMAN) I A Technique for Photographing Difficult Subjects through a Petrographic Microscope. (TP 2092 by DONALD W. SCOTT, Min. Tech., Nov. 1946. Discussion by HORACE WINCHELL) 2 The Search for Concealed Deposits-a Reorientation of Philosophy. (TP 2146 by SAMUEL G. LASKY, Min. Tech., May 1947. Discussion by T. M. BRODERICK)3 Occurrence of Lead-zinc Ore at Iron King Mine, Prescott, Arizona. (TP 21 go by H. F. MILLS, Min. Tech., July 1947. Discussion by HUGH M. ROBERTS)3 Geologic Relations and New Ore Bodies of the Republic District, Washington. (TP 2197 by LAWRENCE B. WRIGHT, Min. Tech., July 1947. Discussion by AUGUSTUS LOCKE and J. A. RICHARDSON) 4 San Manuel Prospect. (TP 2255 by H. J. STEELE and G. R. RUBLY, Min. Tech., Sept. 1947. Discussion by L. KENNETH WILSON, ELDRED D. WILSON and the author) 5] Review of Fluorescence as Applied to Minerals, with Special Reference to Scheelite WALTER W. BRADLEY*-AS I recall, the first portable units for ultra-violet light of practical use with scheelite were developed at the Nevada-Massachusetts Tungsten Mine at Mill City, Nevada, and were used underground. Ultra-violet lamps are also installed there in the mill, above the gravity-concentration tables, for control observations. Geologic Interpretation of Magnetic Exploration on the Mesabi Range, Minnesota ROBERT B. SOSMAN*-When artificial precipitated magnetite is oxidized at a temperature in the vicinity of 100°C, the oxide is converted into a chocolate brown ferric oxide of the formula Fe2O3, free from ferrous iron, yet possessing the same magnetic susceptibility as the original Fe3O4. This form of Fe2O3 is variously called "ferromagnetic ferric oxide," " maghemite," or "gamma ferric oxide," and has been found as a natural mineral. If a body of magnetite in the Biwabik were to oxidize to this form, the oxidized and leached ore body might successfully conceal itself from Mr. Jones' survey by this ferromagnetic pretense. So far, gamma ferric oxide has not been found on the Minnesota iron ranges. I thought I had found some in the Hibbing pit in 1940, in a strongly magnetic specimen of soft ore differing in color from the prevailing hematite

Jan 1, 1947

By AIME AIME

THE 1941 fall meeting of the Iron and Steel and the Institute- of Metal, Division held at the Ritz-Carlton Hotel, Philadelphia, during the first three days (Oct. 20-22) of the National Metal Congress was well attended as usual, and the seven technical sessions and the joint round table on order-disorder transformations were this year of considerably more than routine interest. Despite unseasonably warm weather, a scarcity of hotels (there were rumors, apparently well-founded, that , some of the metal man attending the Congress had to stay in tourist camp), and a multiplicity of technical and other ions of the co-operating societies that gave the Congress this year the general air of a three-ring circus the A.I.M.E. sessions attracted audiences that ragged from seventy or eighty up to 350

Jan 1, 1941

By D. Turnbull, J. H. Hollomon, J. C. Fisher

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]

Jan 1, 1948

By J. M. Sands

Production of oil in Oklahoma during 1927 amounted to 273,256,900 bbl. (Table l), an increase of nearly 100,000,000 bbl. over the previous year. All of the major fields declined with the exception of those of the Seminole district which produced 136,105,000 bbl., almost one-half of the total production of the state. Because of this large new production, most of the development in the state during the year took place in that district. The Seminole City pool located in T.-9-N., R.-6-E., was the first of these pools to be developed. The Indian Territory Illuminating Oil Co. brought in the first well in this field in March, 1926, for 1100 bbl. This well is located in Sec. 24-T.-9-N., R-6-E., and produced from the Hunton lime reached at depth of 3900 ft. The first Wilcox production was developed by the Independent Oil & Gas Co. and R. S. Garland in Sec. 26, T.-9-N, R-6-E. This well was being drilled for production in the Hunton lime but was dry in this horizon and was deepened to the Wilcox sand in July, 1926, and at the total depth of 4069 ft. developed a maximum production of 8000 bbl. daily. It held up in wonderful manner and was the cause of not only the development of this pool but the prospecting of the whole district for the Wilcox sand. This led to the discovery of the other major pools in that district. Seminole City pool reached a peak production of 264,500 bbl. on February 22, 1927, and slowly declined so that by December it had a daily average of 56,200 bbl. from 321 wells. The second pool in this district to be discovered was the Searight pool which was discovered by F. J. Searight et al. in Sec. 33, T-10, R-6, in April, 1926. The first well was drilled to the Hunton lime encountered at 4115 ft., and came in for 1300 bbl. daily. During August, 1926, the second well was drilled on the same farm through the Hunton lime to the Wilcox sand which was encountered at 4360 ft. It came in for an initial production of 4000 bbl. daily. This started active drilling in this field for the Wilcox sand. The field had a peak production of 40,621 bbl. on June 15, 1927, and declined to a daily average of 22,300 bbl. from 73 wells during December.

Jan 1, 1928

Aamot, Olav Crone, Research Engr., Norsk Elektrokemisk Kongensgt, 18, Oslo, Norway ?29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Consolidation Coal Co., Watson Bldg., Fairmont, W. Va. '15 Abel, Raymond L., Asst. Prof., Dept. of Pet. Refin., Univ. of Pittsburgh Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 364 S. Cloverdale Ave., Los Angeles, Calif. '32 Abele, Louis T 1457 Euclid Ave., Zanesville, Ohio. '31 Abell, Leo M Sullivan Concentrator, Chapman Camp, B. C., Canada. '31 Aborn, Robert H., Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. '19 Abraham, W. E. V., East India United Service Club, 16 St. James' Sq., London, S. W. 1, England. '28

Jan 1, 1936

By G. Bassi

RECENTLY Wallbaum¹ found that copper wires with different degrees of deformation up to 98.7 pct area reduction recrystallize giving a [112] texture, while deformation over 98.7 pct gives either a [l00] texture at low temperatures or a [1ll] texture at high temperatures. Furthermore it was found that the recrystallization temperature as a function of deformation up to 98.7 pct decreases as expected, but increases over that deformation. Wallbaum concluded that the different textures have different recrystallization temperatures. The [112] texture has the lowest and [Ill] the highest. At the same time Bassi² found that for high deformation (over 99 pct area reduction) and for an annealing temperature of 400°C, the [l00] texture first forms and with prolonged annealing time the [12] texture appears through grain growth. This secondary texture does not appear if the wire is annealed at 1000°C before the deformation. From these two papers it might be concluded that the [I12] texture can appear either as a primary or as a secondary texture after annealing. The texture formed in a special case depends on the previous history of the wire. Probably the texture of the wire prior to the last deformation is important. To investigate this, wires were produced by adequate deformation and annealing to give a [l00], a [112], and a [lll] texture. The wires then were given a series of different deformations and were annealed at various temperatures, after which the textures were studied. Experimental Work The copper used was electrolytic tough-pitch (Cu 99.90 pct and 0, 0.04 pct). Three wires with the different initial textures were made in the following way: The [l00] and [112] by drawing a 16 mm rod to 1 mm and annealing it 16 hr at 200°C and 2 hr

Jan 1, 1953

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896

Jan 1, 1923

By W. N. Tanner

THE wire-rope hoisting conditions at the mines of the Anaconda Copper Mining Co. in Butte, Mont., are very severe because of the conditions under which it is necessary to operate. A study was made, in the fall of 1919, for the purpose of changing these conditions in order to obtain longer rope and sheave life. There are at present in Butte, hoisting engines equipped with wire rope as follows: 9 main hoists using flat ropes. 7 main hoists using 1 ½ in. rope. 5 main hoists using 1 ¼ in. rope. 6 shafts using 1 1/8 in. rope. 2 chippy hoists using 1 ¼ in. rope. 9 chippy hoists using 1 1/8 in. rope. 15 shafts using 1 in. rope. 7 shafts using 7/8 in. rope. 1 shaft using ¾ in. rope. In addition, there are a number of sinking engines using 5/8 in., ¾ in., 7/8 in., and 1 in. (15.9, 19, 22, and 25 mm. rope.) The flat ropes run from ½ by 7 ½ in. (12.7 by 190.5 mm.) to ½ by 4 ½ in. (9.5 by 114 mm.) and are used on the older hoisting-engines, which are set comparatively close to the shaft. Because of swelling and moving ground at some of the shafts, these ropes present certain difficulties in operation that are more pronounced than with round ropes; they are, therefore, being superseded by round ropes as newer engines are being installed. They are, however, much more easily inspected and repaired than round ropes.

Jan 2, 1922

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896

Jan 1, 1923

By P. M. Robinson, M. B. Beaer

The heat of formation at 0°C of the intermetallic compound AgMg as a function of composition has been determined by tin-solution calorimetry. In this technique, the heat of formation is determined as the difference in the heat effects, at infinite dilution, on dissolution of the compound and a mixture of its components added alternately to liquid tin from a reference temperature, such as 0°C. The experimental technique and method of calculation have been described elsewhere.' The compound AgMg is a 0 electron compound with a CsCl structure.2 In nonstoichiometric compositions of the compound, atoms of the excess component are substituted on the AgMg lattice.3,4 The homogeneity range is approximately 43 to 52 at. pct Mg at room temperature and 38 to 65 at. pct Mg at 500Oc.2 Single-phase alloys outside the homogeneity range at room temperature can be prepared by quenching. The specimens used in this investigation contained from 39.0 to 54.8 at. pct Mg. They were made available, together with analyses, by the Research Laboratory of the General Electric Co. Metallographic examination of the quenched specimens containing 39.0 and 54.8 at. pct Mg gave no indication of the presence of a precipitated phase. The measured heats of formation are listed in Table I. In a calorimetric run, four to six additions each of a specimen and the corresponding mixture of the components were made. One or two calorimetric runs were carried out with each composition depending on the amount of samples available. The limits stated in the table represent the experimental precision and not the absolute accuracy of the measurements. Thermodynamic investigations of the compound AgMg have been made by Trzebiatowski and Terpilowski 5 and Kachi.6,7 The heats of formation at 500°C derived from the combined electromotive-force values of these investigators8 are more exothermic than the heats of formation at 0°C reported here, Fig. 1. The differences cannot be explained by the difference in temperature. This is shown by the published heat capacity of the stoichiometric compound, which obeys the Kopp-Neumann rule from 0" to 500oC.9 The heats of formation derived from equilibrium data are generally considered to be less accurate than those determined by calorimetric methods because small errors in the change of the equilibrium values with temperature have a large effect on the calculated value of the heat of formation. The heats of formation derived from the combined published electromotive-force values reach a maximum at 56.0 at. pct Mg.8 Kachi reports a maximum of -4.7 kcal per g-atom at the stoichiometric composition.7 The present results also indicate a maximum at or near the stoichio metric composition, Fig. 1.

Jan 1, 1964

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf's CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By Alexander L. Field

In the light of the experimental data on equilibrium for the reaction C + FeO = Fe + CO in molten steel recently obtained by Kinzel and Egan,l it is necessary to revise current theories regarding the nature of equilibrium between carbon and FeO in the basic open-hearth furnace. According to the measurements of these investigators the equilibrium constant m for the above reaction for a pressure of dissolved CO equal to 1 atm. is equal to 0.0005 at 1550" C., when concentrations of carbon and FeO are expressed in percentages by weight. Their work also shows that, with the pressure of CO fixed at 1 atm., not only is the product of carbon and FeO constant, but carbon and FeO are each independently constant—a circumstance which might have been predicted from theoretical considerations. At 1550" C., carbon is constant at about 0.025 per cent. and FeO at about 0.020 per cent., with the pressure of dissolved CO equal to 1 atm., the product of these two constants being equal to the originally mentioned constant of 0.0005. Available data on the dissolved FeO content of samples taken from the metal bath at practical slag-metal equilibrium prove that this FeO content is determined solely by temperature and the effective FeO content of the slag. The distribution constant r at 1550" C., as determined by Herty, Gaines, Larsen, Simkins, Geruso and Watkins2 is equal to 0.0086. A slag would have to contain 0.020 = 2.3 per cent. effective 0.0086 FeO or less in order to prevent the metal from containing more dissolved FeO than that required for equilibrium with CO at 1 atm. pressure. Such low percentages of FeO are never found in basic open-hearth slags at the completion of a heat when rate of carbon drop has become practi-

Jan 1, 1930

By F. C. Blake

The best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld'schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide.7 It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results

Jan 1, 1881

By F. R. Hensel

ACCORDING to statements by Guertler,1 Smith and Hamilton were the first to study the copper-titanium alloys, but owing to the presence of large amounts of impurities their data are inconclusive. M. A. Hunter and I. W. Bacon later investigated the electrical conductivity and the temperature coefficients at room temperature. The present writers reported their results2 in November, 1930. Recently Droll published data on copper-titanium alloys3 which agree closely with those obtained by the authors. MATERIAL TESTED The titanium used was in the form of square sintered rods, the analysis of which runs as follows: titanium, 95.4 per cent; silicon, 0.7; iron,1.8; aluminum, 1.4; copper, 0.1; manganese, 0.05. . The ingots were prepared in a high-frequency induction furnace in air atmosphere. Their analyses are given in Table 1. Up to 5 percent titanium the alloys could be forged. Above that amount they were red short and broke up easily. Owing to their rapid absorption of nitrogen and oxygen from the air, the alloys with the higher amounts of titanium tend to form surface films which greatly increase the casting difficulties, especially when small masses of metal are handled. It was, however, possible to prepare sound ingots up to 25 per cent titanium.

Jan 1, 1931

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By Garth M. Crosby, F. McIntosh Galbraith, Bronson Stringham

THE Hercules mine is located in the northeastern section of the Coeur d'Alene district, approximately 1 1/2 miles north of the town of Burke, Idaho. Surface indications of the ore deposit were first discovered in 1886, but regular mine production was not started until 1902 and was continuous until April 1925, when the known ore had been extracted. Incomplete records show that from 1912 until operations were suspended the mine produced 2 1/2 million tons of ore containing 9.4 pct lead and 7.7 oz of silver per ton, together with an estimated 2 pct zinc, 0.3 pct copper, and 20 pct iron. This operation was the first in a series of mining enterprises culminating in October 1947 with the consolidation of Day Mines, Inc. In the same year it was decided to unwater the levels below the collar of the Hercules shaft in the hope of finding some indication of a recurrence of ore. The unwatering operation has been described in a previous paper.1 The initial exploration, following recapture of the workings, showed sufficient promise to warrant a detailed study of the mineralogy with modern techniques.

Jan 12, 1953