Search Documents

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By Craig R. Barrett, Alan J. Ardell, Oleg D. Sherby

It is shown that the apparent activation energy for creep of pure poly crystalline metals increases with increasing temperature in the temperature range 0.5 to 1.0 of the absolute melting temperature. This increase is probably associated with the influence 0-f the elastic modulus on the creep rate. By accounting for the variation of Young&apos;s nodulus with temperature, the true activation energies for creep of pure cadmium and aluminuvl are shown to be equal to the activation energies for self-diffusion in these metals, within experimental error, at all temperatures above 0.5T,. New creep parameters are proposed for cmrelation of steady-state creep rate and time-to-rupture data. These are respectively, where u is the creep stress, E is Young&apos;s rrodulus, i,is the steady-state creep mte, t, is the time -to-rupture, and D is the self-diffusion coefficient [equal to Do exp (-QSd/RT)] . It has been established experimentally1 and theoreticallyZm4 that high-temperature creep of poly-crystalline pure metals is a thermally activated process and may be represented by the general expression where <, is the steady-state creep rate, A is a constant dependent on the internal structure of the material, f is some function of the applied stress (0) and test temperature (T), and D is the self-diffusion coefficient. If D is separated into its temperature-dependent and independent portions, then it is possible to rewrite Eq. [I] as where Qsd is the activation energy for self-diffusion. Assuming a simple Arrhenius-type relationship between creep rate and temperature at a given constant stress, the apparent activation energy for creep, Q,, is given by the expression It is obvious that if is not a function of temperature It has been shown that the steady-state creep rate for pure polycrystalline metals1 can be represented by where S is a constant, L is the grain diameter, E is the isotropic polycrystalline (unrelaxed) elastic modulus, and n is a constant equal to approximately 5 over a wide range of stress. The apparent activation energy for creep calculated from this expression at constant grain size and stress is given by

Jan 1, 1964

By B. A. Wilcox, A. H. Clauer

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967

By B. W. Prof. Frazier

I PROPOSE in this paper to treat of the chimney merely as a heat engine, as one of the devices resorted to in practice for the conversion of heat into mechanical work. For the sake of simplicity and clearness in the discussion, let us consider the subject in its simplest form. Conceive a chamber, heated from without, in free communicatioH at one end with the external atmosphere, and at the other end opening into a vertical chimney. Let the. cross-section of the chamber be so great, relatively to that of the chimney, that we can neglect the actual energy of the air passing through the chamber. We will neglect, also, all passive resistances to the passage of the air. We will assume that the cross-section of the chimney is constant, and that the air in passing through it neither gains nor loses heat. The following symbols will be employed in the discussion : Po = the normal pressure of the atmosphere, which, it is assumed, is the pressure existing at the level of the chamber. Po = 10332.96 kilograms per square meter. P2 = the pressure of the external atmosphere at the top of the chimney. To = the, absolute temperature of melting ice by the centigrade scale. This is assumed to be the temperature of the external air at the level of the chamber. To = 273°. T2 =the absolute temperature of the air as it passes from the chamber to the chimney. T3 =the absolute temperature of the air as it issues from the chimney. to, t2, t3 are the temperatures, as recorded on the centigrade ther¬mometer, corresponding to the absolute temperatures To, T2, T3 re-spectively to = 0° C. In general, t = T- 273. Io, I2, I3, represent the intrinsic energy of the air at the temperatures To, T2, T3 respectively.

Jan 1, 1882

By John P. Hager, Adolfo R. Zambrano

The thermodynamics properties of the liquid Pb-Ag-Au system have been determined from galvanic cell measurments five pseudobinary systems of fixed XAg/XAu ratio. The galvanic cell employed a molten PbO-SiO2 electrolyte and was operated between 775" and 1030°C. The thermodynamics properties of lead were obtained directly from the experimental data, whereas the excess integral molar properties and the activities of silver and gold were obtained by means of the Gibbs-Duhem equation. The calculated proper -ties of the Ag-Au system agree well with the published properties. The liquidus surface of the Pb-Ag-Au system has been determined at 1200°K. In Parts I&apos; and 11&apos; the galvanic cell Mo,Pb(l)|(PbO-SiO2)(l) SiO2(s) |Pb(alloy)(l), Mo [I] was used to determine the thermodynamics properties of the Pb-Ag and Pb-Au systems, respectively. The use of cell I, in which a molten oxide electrolyte is employed rather than the classical fused-salt electrolyte, was shown to result in more accurate ther-modynamic measurements in that the displacement reaction at the alloy-electrolyte interface (l/Zb)B(alloy) + (I/za)A+Za = (1/Za)A(alloy) + (1/Zb)B+zb [1] was minimized. For the Pb-Ag system, where B = Ag(l), the error in the activity of lead (aPd) re-sulting from Reaction [I] was calculated to be less than 1 pct.l For the Pb-Au system the error in aPb was calculated to be less than 0.5 pct.2 Also, electro-transport measurements on the PbO-SiO2 electro-lyte1,2 established that the conduction was entirely ionic and that lead was present only in the divalent state. In the present study the experimental technique is extended to an investigation of the thermodynamic properties of the liquid Pb-Ag-Au system. Five pseudobinary systems of fixed X Ag/XAu ratio were selected. The experimental results were then combined with the previous measurements on the component binary systems Pb-Ag1 and Pb-AU2 to calculate, by means of the Gibbs-Duhem equation, the molar and partial molar mixing properties for the liquid ternary solutions.

Jan 1, 1970

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946

One-half fare return rate again available to members of the Institute and dependent members of their families. DON&apos;T FORGET YOUR RAILROAD CERTIFICATE Over 300 members of the A. I. M. E. and dependent mem-bers of their families attending the last annual meeting se-cured return railroad tickets at half price by means of the railroad certificate, thereby saving several thousand dollars. DIRECTIONS 1. Be sure to obtain your railroad certificate when pur-chasing your railroad tickets for the meeting or you will lose money. 2. Purchase your tickets at regular one-way adult tariff fare between the dates specified for your territory in the accom-panying table. 3. Present your certificate for valida-tion at Institute headquarters in New York immediately after registration. Certificates will be validated on Feb. 21 and 22 between 9 a. m. and 5.30 p. in. 4. You must use your return half-rate tickets not later than Feb. 27. 5. Use the same route for both going and return trip. PLEASE REMEMBER THIS 1. Unless-250 certificates are validated at headquarters it will be impossible for anyone to secure the reduced rate. 2. Unless you secure a certificate you cannot take advantage. of the half-rate return fare, even if the necessary 250 certificates are validated.

Jan 2, 1928

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By J. Chipman, J. C. Fulton

Reduction of silicon from blast-furnace-type slags by carbon-saturated iron is a very slow reaction even under conditions of rapid stirring. Equilibrium under atmospheric pressure of carbon monoxide was approached from both sides, and the silica-silicon relation was established at temperatures of 1425º to 1700°C for slags containing up to 20 pct Al2O3. Silicon carbide is formed by reaction of graphite with high silica slags and the conditions for its formation were determined. Activities of SiO2 and of CaO in their binary solutions at 1600°C were determined. The effects on the activity of SiO2 were established for additions of 10 to 20 pct AI2O3 and of 10 pct MgO. STUDIES of chemical reactions between blast-*>-5 furnace slags and metal have been focussed on the transfer of sulphur from metal to slag. The important role which silica reduction plays in this process&apos; has led to a study of the transfer of silicon from slag to metal and the equilibrium represented by the equation SiO2 (in slag) + 2C (graphite) = Si + 2CO (g). [I.] The authors2 have published an account of the experimental method employed in attacking this problem and of three series of experimental results at 1600°C. This paper contains data on some additional compositions and extends the observations to cover the temperature range 1425° to 1700°C. The data are used to determine the activity of silica in the slags. As in the earlier experiments, the atmosphere was carbon monoxide which flowed through the furnace at 150 ml per min. In certain heats designated in the tables and figures, the gas was bubbled through the melt using a graphite tube. The latter increased in porosity during a run and in some cases bubbling ceased as indicated by cessation of surging. Some results were discarded for this reason. Experimental Results The new data are shown in Tables I through V and both old and new data are plotted in Figs. 1

Jan 1, 1955

By D. S. Jacobus

It is proposed to give in this paper an estimate of the cost at which carburetted and uncarburetted water-gas will have to he sold, in order to compete successfully for steam-boiler use with anthracite coal. The following are analyses of the gas direct from the generator, and of the same after it has been carburetted for illuminating pnrposes. Per cent. by Volumes. I. 11. Uncarburetted. Carburetted. Nitrogen,.4.69 2.5 Carbonic acid,.3.47 .3 Ethylene,....... 0 12.5 Oxygen,....... 0 .2 Benzole vapor,...... 0 1.5 Carbonic oxide,.36.80 29.0 Marsh-gas,.2.16 24.0 Hydrogen,.52.88 30.0 100.00 100.0

Jan 1, 1889

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information&apos; on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information&apos; on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By C. A. Stewart

PAGE. I. Introduction............ 241 II. Location. TopoGRaphy. and History....... 243 III. DescRiption of the Rocks......... 245 1. Altered Sediments.......... 245 2. Alaskite........... 246 3. Alaskite.Porphyry.....255 4. Quartz Dikes........... 257 5. Biotite.Granite.......... 256 6. Quartz.Porphyryl......... 260 7. Andesite........... 262 8. Miscellaneous Dikes......... 263 IV. Age oF the Rocks and Comparison with other Localities.. 263 V. AlteRation............ 265 1. Sericitization........... 265 2. Silicification........... 266 VI. StRuctuRes........267 1. Dip of the Limestone......... 267 2. Faulting........... 267 VII. Contact - metamorhism,.......... 269 1. Endomorphism.......... 269 2. Exomorphism......... 271 Recrystallization and Loss of Color...... 271 New ,Minerals.......... 272 Addition of Material........ 274 Volume.Changes.... 276 Locus of Metamorhism........ 277 Method of Precipitation.........278 VIII. ORe-Deposits............ 278 1. Contact-Metamorphic Copper.Ores,..... 279 General..........279 Shape and Distribution........ 279 Minerals........... 281 Secondary Enrichment........ 282 2. Disseminated Copper.Ores........ 283 3. Origin of the Copper.Orcs........ 284 4. Lead-Silver Ores.......... 287 IX. Bibliography............ 288

Jan 1, 1913

R.. B. T. KILIANI, New York, N. Y.-I do not care to discuss Mr. Taggart&apos;s paper in the light of theory, as that has been very well done by Prof. Bell,1 but I should like to criticize some of his conclusions, in the light of actual operating practice at plants all over the country. 1. Mr. Taggart&apos;s first conclusion is that in crushing average ore, the character of the gangue has little effect on the efficiency of the mill. This, I believe, is not in accordance with the usual practice, since in crushing a hard ore the capacity will be much reduced below what it would be with a softer ore, while the power consumed will be practically independent of the character of the ore, being proportional only, to the load of ore and balls in the mill. 2. Mr. Taggart&apos;s second criticism is that the Hardinge mill is not suitable for grinding soft, tough material. In answer to this I might mention that the mill is being used for grinding tough, dnctile material, such as metallic aluminum, and also for grinding licorice root. 3. He says that the ball-mill works more efficiently on material of intermediate size, say 1/2 to 3/4 in., than on either coarser or finer feed.. This is true as to coarser feed. For the most efficient work, I believe that a ball-mill should be fed with material not coarser than 1 1/2 in.; it&apos; will handle material up to 3 and even 4 in., but the reduction from 3 or 4 in. to 1 1/2 in. can be done much more cheaply and efficiently by rolls or disk crushers than in the ball-mill. 4. As to Mr. Taggart&apos;s fourth conclusion, that a greater ratio of reduction can be expected with feed of an intermediate size than with a coarse feed, I have not enough information to express an opinion. 5. His next conclusion is that steel balls are much more efficient crushing media than pebbles. Steel balls are undoubtedly more efficient for crushing coarse feed. On fine material they are also more efficient as to tons per horsepower crushed to 10-mesh, but on fine material I think it will be found that flint pebbles are cheaper than cast-iron balls, per ton of ore, although there will be a saving in power per ton by using cast iron instead of flint. The increased cost of crushing with cast iron will be due to the higher cost of iron at the present time. 6. Mr. Taggart&apos;s sixth conclusion coincides with present practice, that steel balls will grind as fine or finer than pebbles when working on the same feed.

Jan 1, 1918

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.&apos; Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965

By Charles M. Rolker

The Mariposa estate, a grant made by the Mexican Government to Juan 13. Alvarado, during the time when California was still under the dominion of Mexico, was purchased in 1847 by J. C. Fremont, and the United States patent issued to him in 1856. By sale, or its equivalent, money advanced, the property came into the hands of the Mariposa Company, June 25th, 1863, and through a varied existence of work and temporary inactivity, has as yet been kept as an undivided property, and rests at present with the Mariposa Land and Mining Company of California. I pass over this period of 15 years without giving the history of the ups and downs of the estate, partly because it is familiar to many, and also because I think in such a case this paper would assume too much the character of a narrative. The estate is situated in Mariposa County, California, about 170 miles southeast of San Francisco. It begins in lat. 37&apos; 26&apos; 38&apos;&apos; north, and long. 119&apos; 55&apos; west, and runs 6 miles north; thence 69 miles west; thence 5 miles northwesterly towards the Merced River; thence 84 miles southerly; thence 3 miles easterly; thence 1 mile southerly; thence 2 miles easterly; thence 2 miles southerly; thence 2 miles easterly; thence 1 mile southerly; thence 2 miles easterly; thence 1 mile northerly, and thence 2 miles easterly to the place of the beginning; embracing 44,387 acres (70 sq. miles) more or less. To describe this vast estate in detail as to its full geology, its numerous quartz veins, its many facilities to exploit them and work them by cheap methods, would lead me further than I intend to go at present, and I will content myself to describe the latest workings of the company and its immediate field of operations. As long ago as 1860 the late Dr. Adelberg advised the running of an adit from the northwestern edge of the estate at Benton Mills 011 the Mereed River. His object was to undercut the deepest workings of the then paying mines on the estate—the Pine Tree and Josephine. Following this advice, the tunnel known as "River Tunnel " was commenced. Its entrance is in S. 5, T. 4, s. R. 17 E. It is run in

Jan 1, 1879

By Hugh Marriott

MANGANESE and its ores have been recently dealt with in comprehensive papers to the Iron and Steel Institute by Sir Robert Hadfield, and in a series of papers read before the A. I. M. E. at the Cleveland meeting. I have taken the opportunity of adding this mineral, to my records of the "World&apos;s Mineral Production and Consumption," as recently pub-lished in the Economist ?. The tables bring out the following significant facts: The world&apos;s production has increased by 10 per cent since 1913. India&apos;s production has increased by 3 per cent since 1.913, the supply from this source now being 31.1 per cent of the world&apos;s output. Russia is now producing at about half its pre-war rate and yields 19 per cent of the world&apos;s production. West Africa supplies 12.5 per cent of the world&apos;s total output. Brazil&apos;s present output is 2.5 times that of the pre-war period, being 11.3 per cent of the world&apos;s output.

Jan 9, 1927

By R. T. Hukki

THE accepted basis of comparisons between mills of different diameter is the percentage critical speed. If n = actual mill speed, rpm, nc = calculated critical speed, rpm, np = calculated percentage critical speed, and D == inside diameter of the mill in feet, then n, In the following analysis capacity, T, is expressed in short tons per hour, tph, and power consumption, P, in kilowatts, kw. Accordingly power consumption per unit of capacity, P will be expressed in kilowatt hours per short ton, or kw-hr per ton. In all equations D refers to the inside diameter of the mill in feet and v to the peripheral speed of the mill in feet per minute inside the liners. &apos; Comparison between separate mills must be based on equivalent grinding conditions, i.e., same feed, same size distribution of feed, same size distribution of product, and same percentage of solids. In addition, comparisons between separate rod mills must be based on the same rods, same type of liners, and same percentage rod load. Comparisons between separate ball mills presuppose the same balls, similar liners, and same relative ball load. The practical np-range through which the equations apply varies, being narrower for fine grinding in ball mills and wider for coarse crushing in rod mills. The Relationship between Capacity and Speed It is the general belief that the capacity, T, of a tumbling mill is directly proportional to the speed of the mill, other things remaining constant.&apos; Mathematically this is represented by the equation T - c¹ n tph [4] where c, is a factor related with the grinding characteristics of the ore, method of reduction, and the units chosen. It is proposed here that the general equation relating mill capacity and speed should be of the form T = c¹ nm tph [5] In other words, the capacity should be proportional to the mill speed raised to power m, the numerical value of the exponent being 1 5 m 5 1.5, depending on the circumstances. Eq. 5 can also be written in the following forms: T = c, (np)m tph, and [6] T=Ca vm tph, [71 where v = peripheral speed of the mill in feet per minute. If the observed capacity of a mill at speed n¹ is = T¹ tph, the capacity T² of the same mill at speed n² should be T² = T¹ (n²/n¹)tph [8] The Relationship between Power Consumption, Mill Diameter, and Speed The only well known theoretical deduction relating power consumption, P, and mill diameter appears to be the formula of duPont introduced by Gow, Guggenheim, Campbell, and Coghill.&apos; According to duPont, the power required to operate a mill is a function of the mass of the balls, of the lever arm of the ball mass, and of the speed of the mill. The ball mass per unit of mill length is proportional to the square of the diameter, the lever arm is directly proportional to the diameter, and the critical mill speed or any percentage thereof is inversely proportional to the square root of the mill diameter. Following this reasoning, the original duPont formula is of the form P = c4D² c D • c6D-0.5 = c7D2.5 [9] If the mill speed in the above equation is expressed in terms of Eq. 3, the duPont formula may be written as follows: P=f1(D2) f2(D) f³(—np) or [10] vD P = c np D2.5 kw [11] Eq. 11 may also be derived from the mechanical principle of force, which is equal to mass x acceleration. Power necessary to operate a mill may be considered to be an homogeneous linear function of the force developed. Ball or rod mass per unit of mill length is a function of D2. The acceleration factor of the ball or rod mass is a function of the peripheral speed of the mill. Thus P = f4(F) = /x(D2) f5(v) Indicating that v = nDn, and n = c9 np /vD, the above equation becomes P = f2 (D2) -fa (D ca np/vD

Jan 1, 1955

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962