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By Rossiter W. Raymond

In the case of The Eureka Consolidated Mining Company v. The Richmond Mining Company of Nevada, recently tried at San Francisco, California, the real defendant was the Richmond Consolidated Mining Company, of London; but this being a foreign corporation, holds its mining property in Nevada through the Nevada corporation of similar name, in which the London Company owns all the stock, except the few shares necessary to " qualify" the American directors. The trial would naturally have taken place in the Circuit Court at Carson City, Nevada, and before a jury. But by stipulation of the parties, the case was tried in San Francisco, before Hon. Stephen J. Field, Justice of the Supreme Court of the United States, Hon. Lorenzo Sawyer, United States Circuit Judge of the Ninth Circuit, and Hon. E. W. Hillyer, United States District Judge, for the District of Nevada. The hearing began July 23d, 1877. The witnesses occupied two weeks, and the argument of counsel three days. Very eminent lawyers were engaged on both sides; for the plaintiff, Messrs. Solomon Heydenfeldt, R. S. Mesick, John Garber, and H. J. Thornton; for the defendant, Messrs. S. M. Wilson, Thomas Wren, and J. J. Williams. The court held the case under advisement until August 22d, when Mr. Justice Field delivered its unanimous opinion in favor of the plaintiff. The action was a complaint in ejectment, and an appeal was taken to the United States Supreme Court. The questions at issue between the Eureka and the Richmond Company in this suit, comprised several points in the construction of the mining law of the United States, and its relation to the customs and regulations of the mining districts, which possess an importance and an applicability far beyond the limits of the case in which they arose. It is my purpose to state these points, the arguments

Jan 1, 1879

By Richard W. Lodge

Ix the crucible-method of assaying ores for silver a certain amount of litharge is essential to supply sufficient lead to collect the precious metals. The object of this paper is to point out that the use of a .large excess of litharge in the assay of some ores will give results for silver that are uneven as well as low. So far as I know, however, an excess of litharge does not affect the results obtained in the crucible-assay of ores for gold. The main reasons for using, in the crucible-assay, much more litharge than is required to give the necessary lead button are : 1, its action as a flux; 2, its action as a desulphurizer; and 3, its action as an oxidizer, especially on metals like copper and nickel, whereby they are forced into the slag as oxides and thus prevented from passing into the lead button. Hence, by the use of much litharge in the crucible-assay more-ore can often be taken than in the scorification-process, and a lead button obtained which can possibly be cupelled at once or after a single scorification. The method is specially advantageous with an ore carrying much copper or similar impurity and poor in silver, when the assayer does not wish to resort to a wet-analysis for the determination of the silver. It is well known that some ores give better results when assayed by the scorification-method, while others give better results by the crucible-method. For several years I have noticed that, when much litharge was used with certain sulphide and arsenical ores, the results were considerably lower than when the scorification-method was used. This fact was more forcibly brought out in connection with certain work carried on this year by Messrs. H. A. Frame and

Sep 1, 1907

By Earl Bardwell

(Butte Meeting, August, 1913.) THE structural relations existing between cuprous oxide and copper were first systematically studied by Heyn1, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming .;from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study off the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing, this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in, this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity.

Jan 7, 1913

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By V. F. Swanson

At the AIME meeting in Tampa in Oct. 1966, an empirically developed equation was presented which allowed the calculation of free settling velocity for any sized particle: 1 [ ] This equation requires the use of two parameters a and p which are coefficients derived from boundary layer theory.2 It was possible to develop values of a and p for several minerals by back calculation of published data. The original equation had one major flaw. When the fluid density exceeds the density of the solids, the solution to the equation becomes imaginary. A flaw was indicated also by the fact that galena and sylvite both having cubic cleavage, did not have similar values for a and b. Galena gave calculated values of a = 1.082 and g = 3.11, while sylvite gave values of a = 1.870 and p = 2.56. These flaws prompted further study of the equation, resulting in the following empirical modification: [ ] It is obvious a real solution of the equation is possible for all values of ps and p. When PL > PS, V is negative, indicating that the particles will rise against the attraction of gravity. The validity of the modification is borne out by the fact that when values of a and p were back calculated for galena and sylvite using the modified equation, both minerals gave values of a = 1.038 and p = 3.01. With the modification shown in Eq. 2, Newton's friction factor becomes [ ]

Jan 1, 1976

By A. Wadood M. A. El Rabaa, William A. Hustrulid, William F. Ubbes

The spatial distribution of the deformation modulii around the CSM/ONWI test facility was determined using an NX version of the CSM cell. Approximately 840 modulus measurements were made in six rings (each ring containing seven holes each 6 m in length) of boreholes. These parallel rings were spaced at 2.4 m intervals along the room. Contour plots of the modulii revealed that the depth of the blast damage zone varied both with perimeter position and distance away from the opening. The maximum depth of disturbance appeared to be of the order of 60 cm. At locations removed from the opening, the variability in modulus was quite high reflecting the presence of joints, faults, shear zones and foliation. A comparison of rock mass modulii (ER) with those obtained from the laboratory testing of core (E), revealed that ER [=] 0.5 E.

Jan 1, 1982

By Eduardo J. Chibas

Location.—The principal manganese-deposits of the Department of Panama, Republic of Colombia, are located almost clue south of Viento Frio, a native village bordering on the Caribbean Sea, and about 45 miles northeast of Colon (Aspinwall). The mining-claims are the Viento Frio, the Carrano, the Nispero, and the Soledad. Each property is to the south of the preceding one in the order mentioned. The first one is about one mile from the coast, and the most southerly boundary of the Soledad is about five miles in a straight line from the same coast-line. I shall confine my remarks to the four properties mentioned and to La Guaca, west of the Carrano, because these are the only ones where mining has so far been done to more or less extent. Manganese has also been found, however, in the neighborhood of these deposits, and a large area adjoining them has been divided into sections and " denounced " as mining-claims. The relative position of the manganese-deposits and Nombre de Dios, the present terminal of the railroad and shipping-port, as well as Viento Frio and the adjacent coast, can

Jan 1, 1898

By H. C. Fiedler

SILICON-IRON strip with a cube-on-edge secondary recrystallization texture is made commercially as thin as 10 mils. With inclusions present to inhibit normal grain growth, a few grains, and these have the (110)[001] orientation, grow very large at the expense of the matrix grains. In the absence of inclusions, only normal grain growth occurs and the texture is not as strong as when it is developed by secondary recrystallization.1 Strip for use at frequencies of 400 cps and higher is made in thicknesses of 1, 2, and 4 mils by a process developed by Littmann.2 Attempts to develop a strong texture in these thin gages by the same methods as were used for the 10 mil and thicker strip were unsuccessful,2 and Littmann's solution to this problem was to cold roll the grain

Jan 1, 1963

By J. J. Frawley, W. J. Childs

Experiments were carried out to induce grain refinement during solidification by applying vibrational energy (freq 20 kc) to small specimens of bismuth, tin, and bismuth-tin alloys. The results show that if the intensity of the applied sound -field is not great enough to fragment the growing dendrites of a pure metal, no grain refinement is observed and the pain size of the dynamically nucleated specimens is the same as the grain size of a specimen statically supercooled the same amount. Bismuth specimens did not show any grain refinement; whereas, the tin specimens did show grain refinement. This phenomenon is the result of the difference in growth habit between the bismuth and tin dendrites. The bismuth-tin alloys showed grain refinement and, in addition, the segregation pattern was changed. THE solidification process is a change in phase requiring the nucleation of the solid phase from the liquid and the growth of this solid phase at the expense of the liquid phase. Since many physical properties and also the integrity of a casting are dependent on the solidification process, understanding and controlling this process are very important.' A good example in the controlling of a cast structure using heterogeneous nucleation theory is the reduction of grain size in aluminum castings by nucleation catalysis.2 This mechanism of nucleation catalysis has been explained by Turnbull.3 Another technique for grain refinement, which has received much attention but the mechanism has not been fully understood, is to vibrate the solidifying melt. Vibrations can be applied to the melt either by vibrating the mold directly or by introducing a vibrating rod into the melt.4-13 Three mechanisms have been proposed to explain this phenomenon: 1) The mechanical fragmentation of the original dendrites that grew into the melt. These crystals or fragmented dendrites act as new growth sites. 2) The nucleation of new grains in the liquid by the generation of very high pressure pulses caused by cavitation in the liquid. 3) The remelting of the dendrite arms during the solidification process. This mechanism is operative only in alloy systems and would be enhanced by stirring or mechanical vibration. The purpose of this investigation was to determine the mechanism that will increase the number of grains when mechanical energy is introduced into a solidifying melt. APPARATUS The unit used to generate the ultrasonic vibrations was manufactured by the Redford Co., and is similar to the one used in ultrasonic soldering. Fig. 1 is a sketch of the major components used for generating ultrasonic vibrations. The crystal transducer assembly consisted of four lead zirconate ti-tanate piezoelectric crystals in an aluminum holder. An acoustical horn, which was fabricated from stainless steel, was attached to the holder by a set screw. The resonant frequency of this unit was 20,000 cycles per sec. A Pyrex crucible, 4 in. in diam and 4 in. high, was contained in a hole in the top of the horn. The piezoelectric crystals changed volume when excited by an electric signal, thereby generating a sound signal which passed through the horn. The crucible was coupled to the horn by a liquid silicone oil. The purpose of the couplant was to transmit the soundwaves from the horn to the crucible. Without the couplant, much of the sound energy would be lost. The energy transmitted was sufficient at the resonant frequency used, so that acoustical cavitation always occurred in the molten metal. The presence of acoustical cavitation was detected by the characteristic hissing sound emitted from the liquid. EXPERIMENTAL PROCEDURE The influence of ultrasonic vibration on the grain refinement of bismuth, tin, and bismuth-tin alloys was studied. These metals were chosen because of their low melting temperature and the relative ease with which they can be thermally supercooled. The following procedure was used for obtaining large amounts of supercooling. Pure bismuth (99.999+), which was received in bar form, was mechanically broken into pieces small enough to be accommodated in a 50 ml beaker. About 200 to 300 g of bismuth and a few grams of SnCl2 as a flux were placed in the 50 ml beaker and melted by induction heating. The melt was held for 20 min at

Jan 1, 1970

Abbey, Robert Graham, District Mgr.. The W. W. Sly Mfg. Co., 50 Church St.. New York, N. Y. '21 Abbott, A. N., Mines Supt., Mazapil Copper Co., LtdConcepcion del Oro, Zac., Mexico. '28 *Abbott, Argyle Campbell, Dev. Dept., E. I. du Pont de Nemours & Co., Wilmington, Del. '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., Elkhorn Div., Consolidation Coal Co., Jenkins, Ky. '16 Abeel, George H., Jr., Cons. Min. Engr Box 427, Santa Monica, Cal. '18 Abel, Albert E., Asst. to Pres., Valley Mould & Iron Corp Hubbard, Ohio. '19 Abel, Raymond L., Asst. Prof., Dept. of Pet. Refin., Univ. of Pittsburgh Pittsburgh. Pa. '28 Abeel, Leo M., Research Engr., Sullivan Concentrator Chapman Camp, B. C., Canada. '31

Jan 1, 1929

By O. A. Knight

THE suppression of the austenite-martensite transformation that can be brought about by the addition of certain alloying elements, such as manganese or nickel, to plain carbon steel has been known for a long time, especially since Guillet's investigation at the beginning of this century. The extent to which the critical range is lowered depends upon the percentage and nature of the special element added. First the Ar1 point is lowered gradually, then at a certain percentage a sudden lowering to about 300° C. occurs. The addition of still larger percentages of the alloy may result in lowering the Ar1 point to room temperature or below, in which case the steel remains austenitic at room temperature, especially after rapid cooling. The effect of alloying elements of this general type on the lowering of the transformation temperature is well illustrated by Sauveur(1)§ in his Fig. 281a, reproduced here as Fig. 1. This type of curve is characteristic of both manganese and nickel though it requires about 2 1/2 times as much nickel as of manganese to produce the same result. The influence of nickel in retarding the transformation of austenite into the lower transition constituents is due to its lowering of the critical range of the steel, which is also well illustrated by Sauveur(1) (after Osmond) in his Fig. 284, reproduced here as Fig. 2. Scott(15) presents a diagram illustrating the effect of manganese on the Ac3 and Ar3 points which is strikingly similar to the diagram above referred to in Fig. 2 concerning the effect of nickel.

Jan 1, 1934

By Otto Henry

THE purpose of this investigation was to determine the equilibrium diagram of the lithium-magnesium pair as a first step in studying the possible usefulness of these alloys as ultra-light structural materials. REVIEW OF THE LITERATURE The behavior of lithium towards magnesium was first investigated by Masing and Tammann.(I)? In order to prevent oxidation the alloys were made in iron tubes under an atmosphere of hydrogen; temperatures were measured with a glass-protected thermocouple. These investigators found that lithium and magnesium form two series of solid solutions separated by a miscibility gap between 85 and 95 per cent magnesium; that the alloys with 81 and 95 per cent magnesium showed a homogeneous structure under microscopic examination, while the alloy with 89 per cent magnesium contained two distinguishable crystallites; that the curve indicating the beginning of crystallization rises from the melting point of lithium to that of magnesium; and that no compounds of lithium and magnesium are formed. The equilibrium diagram was not plotted because no definite data were obtained for determining the solidus and the posi-tion of the miscibility gap in the solid state. The difficulties encountered in this investigation were: (1) that it was necessary to heat them as high as the melting point of magnesium in order to obtain homogeneous melts; at such temperatures the alloys attacked the glass protecting the thermo-couple; and (2) that at temperatures above 400° C. the lithium united

Jan 1, 1934

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat&apos; who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E&apos; and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200&apos;C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By J. Gordon Parr, L. P. Srivastava

DUWEZ1 has shown that pure titanium and pure zirconium transform martensitically during rapid cooling at temperatures about 30° and 15°C re spectively below their To temperatures. Holden et al.2 determined M, temperatures of Ti-Cu alloys by a metallographic technique applied to isothermally treated samples. Their results, superposed on the McQuillan3 version of the partial Ti-Cu diagram are shown in Fig. 1. Sources of metals were: Titanium: Iodide bar; Foote Mineral Co. Ltd. Zirconium: Iodide bar; Foote Mineral Co. LM. Copper: Spectrographic Standard; Johnson Matthey and Co. Ltd. Alloys were prepared by levitation melting under argon to the following nominal compositions:* 0.5, Quenching, at rates to about 8000°C per sec, was performed by cooling in a stream of helium (99.999 pct pure) a 3/64 in. cube of material previously heated by a tungsten coil in a system operating at. 10-5 mm Hg. Cooling rates below 200°C per sec w were obtained by controlling the current to the heater coil. The specimen was supported on a 32 gage Pt, Pt-Rh thermocouple attached through a DC amplifier to an Edin magnetic oscillograph (Model 8082) with a maximum chart speed of 250 mm per sec. Transformation temperatures were read off the oscillograph charts at the location of the beginning of the thermal arrest. The same specimen was quenched several times, and all runs were repeated on new samples. Regular calibrations of the oscillograph against a potentiometer were made between quenching experiments. The criterion of martensite formation was the effect of surface rumpling. Previously polished samples that showed a rumpled surface after transformation are assumed to have undergone martens itic transformation: transformations of a diffusion type produce no surface disturbance, Figs. 2 and 3. Electrochemical measurements were made in a cell described elsewhere4 whose electrodes were the martensitic and the diffusion-transformed materials in the following electrolytes:

Jan 1, 1962

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations&apos;j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.&apos; Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.&apos; Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini&apos;s work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

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

Application of the concepts of nu-cleation and growth to the analysis of experimental transformation data has led to valuable descriptions of phase transformations, an outstanding example being the transformation austenite —* pearlite which has been examined with particular care by Mehl and co-workers.&apos;-5 In addition to the pearlite transformation, the proeutectoid fer-rite and proeutectoid carbide transformations are known to proceed by nucleation and growth. Martensite, on the contrary, until recently was thought to form by a mechanism involving neither nucleation nor growth; however, extension of standard nucleation theory6 suggests that martensite, bain-ite, and the other products of austenite decomposition all grow from nuclei in the parent phase. The theory that martensite forms by nucleation and growth is strongly supported by recent experimental work of Kurdjumov and Maksimova.7 The concepts of nucleatioli and growth have been fruitful also in providing a sound basis for quantitative theoretical treatments of the kinetics of phase transformations. For example, Volmer and Weber8 and Becker and Döring9 developed the theory of nucleation from fundamental considerations to a point where excellent agreement was obtained with the results of experiments on the condensation of supercooled vapors. As a result of their analysis, the kinetics of vapor-liquid transformations now can be predicted. It seems probable that application of the theories of nucleation and growth to a quantitative study of austenite decomposition similarly will clarify the nature of the individual transfor: mations involved, and will enable the calculation of austenite transformation kinetics. In the present paper, the theories of nucleation and growth are applied to the austenite ? martensite transformation in steels. The analysis begins with a discussion of nucleation in single component systems. Martensite appears to be coherent with the parent austenite, hence the nucleation theory is modified to include the effects of elastic distortion. Nucleation in the two component iron-carbon system then is discussed, for most steels are primarily alloys of these two elements. Finally, M. temperatures and martensite transformation curves are calculated for each of several alloy steels of varying carbon and chromium content, and are compared with those determined experimentally by Lyman and Troiano10 and Harris and Cohen.11 Nucleation Theory NUCLEATION IN SINGLE COMPONENT SYSTEMS6,12-14 The work required for reversible formation of a region of phase within the parent a phase is expressed conveniently as the sum of two terms: W1 = Aa, the product of the area of the interface and the interfacial free energy, and W2 = VAf, the product of the volume of the region and the free energy increase per unit volume associated with the transformation. The total work is therefore W = Aa + VAf. When a is more stable than ß, Af is positive and W increases without limit as the volume increases. The transformation a ?ß does not occur. It is nevertheless true that small regions of phase ß enjoy temporary existence here and there in the a. The equilibrium number of ß regions of given size is proportional to exp(— W/kT) per unit volume of a, assuring that larger (ß regions occur with diminishing probability. When a is less stable than ß, Af is negative and W passes through a maximum as V increases. Assuming for simplicity that regions of ß are spherical, as is true when the interfacial tension is isotropic and there are no elastic strains, W = 4r2a + (4/3)*r3Af The maximum value of W is W* = 16iro3/3Af2 [1] for regions with radius r* = -2o/Af. [2] For single component condensed systems it has been shown14 that the steady rate of nucleation of 0 per unit volume of untransformed a is nearly proportional to exp[- (W* + Q)/kT] where Q is the activation energy for the unit processes of adding or removing one atom from an embryo or nucleus. If To is the temperature at which a and ß are in equilibrium, the rate of nucleation is a maximum at a temperature 0 < T < To where (W* + Q)/kT is a minimum. P regions smaller than critical size are called embryos; they tend to grow smaller and disappear, only exceptionally growing larger. Regions equal to or larger than critical size are called nuclei. A critical size nucleus may grow indefinitely large or may shrink back to a, either process decreasing the free energy of the region.

Jan 1, 1950

Established as Mining, Geology and Geophysics Division, Sept. 27, 1949 Name changed February 19, 1958 Robert J Lacy, Chairman John G Hall, Assistant Chairman Vice-Chairmen Peter Joralemon, Membership J M Ehrhorn, Program John C Wangaard, Publications A W Ness, Secretary American Smelting & Refining Co 600 Crandall Building Salt Lake City 1, Utah

Jan 1, 1960

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author&apos;s Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A&apos;) but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968