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Dimitri Konstantinovitch Tschernoff, was horn in Petrograd, Russia, on Nov. 1, 1839, and died in Yalta (Crimea) in the south of Russia, on Jan. 2, 1921. He obtained his early education in the Russian Gymnasium, corresponding to the American high school, and in the Technologic Institute. On graduation from this Institute in 1858, he was engaged as a professor of geometry and algebra and later became a librarian and superintendent of the museum in the same Institute. He also attended lectures in the mathematical physics section at the Univrrsity of Petrograd from 1859 to 1862. In 1866, Professor Tschernoff left the Technologic Institute and entered the employ of the Obouchoff steel plant, founded in 1863 for the manufacture of guns. Here he did his most important work on the heat treatment of steel, its crystallization and metallography. In 1880, he left the Obouchoff plant and went to the south of European Russia, where he discovered and developed some rock-salt mines. This enterprise brought him a rather large fortune. In 1884, he returned to Petrograd and during the next four years held several prominent positions in government departments. In 1899, he became professor of metallurgy in the Michael Artillery Academy, and retained that position until the time of the Russian Revolution. In 1902, Professor Tschernoff was elected an honorary member of the American Institute of Mining and Metallurgical Engineers. In September, 1917, Professor Tschernoff was sponding his vacation, as usual, in the city of Yalta (Crimea) in the south of Russia, with his wife and one of his daughters. The revolution progressed so rapidly that they were unable to return to Petrograd, and were compelled to stay in Yalta without provision for the winter season. Suffering from hunger. and lack of sufficient clothing, and deprived of his books, Tschernoff nevertheless continued his studies and gave a number of lectures on steel at the Polytechnic Institute. At the same time he worked hard on some. mathematical problems. His health broke down through long-continued under-nourishment. His works in the metallurgical field are well known to the students of metallurgy; good abstracts of his most important papers were published in Revue de Metallurgie (1915, pp. 829-882) in commemoration of his 75th birthday.

Jan 1, 1922

Jan 1, 1958

By M. E. Fine

THE electrical conductivity (a) and the thermal conductivity (K) of metallic conductors, as demonstrated by Smith and Palmer1 and Hume-Rothery,2 are to a good approximation related by an empirical equation, K = A s T + B, in which T is the absolute temperature, and A and B are constants, the Lorenz constant and the lattice con- ductivity. Strictly speaking, the lattice conductivity is not a constant, but to some extent depends upon the electronic conductivity.3 By plotting K as a function of sT, this equation has been proved to a

Jan 1, 1951

By Robert F. Mehl, Dana W. Smith

It has been shown that quenched iron of high purity exhibits a Wid-manstiitten figure much resembling martensite in appearance.1 This figure exhibits a maximum of four directions of the surface traces that characterize it, suggesting that a Fc forms from y Fe in plates parallel to the (III), octahedral, planes in the y lattice. Because of this, and also beqause of the general similarity to the structural appearance of martensite and to the Widmanstatten figure obtaining in slowly cooled hypoeutectoid steels it has been suggested2 that the orientation relationships obtaining between the y and a phases in pure iron are identical with those demonstrated in martensite3 and in slowly cooled hypoeutectoid steels,4 and indeed that the crystallographic mechanism of formation of a Fe from y Fe is the basic mechanism determining the orientation relationships found in both martensite and in slowly cooled hypoeutectoid steels. This paper will present experimental evidence in support of this view. Experimental Technique The analysis of the crystallographic mechanism of transformation in pure metals is beset with special difficulties, though some information

Jan 1, 1934

The following is a list of members who died in 1928. It is compiled from reports to the Secretary's office. Biographical sketches published in Mining and Metallurgy are indicated in the last two columns. Issue Containing Year or Date or Biography Election Name Death 1928 Page 1914 Adams. David T.................... July 22 October 471 1905 Aguilera. Pedro................... May 3 October 469 1902 Althouse, H. W.................... NOV. 3 December 559 1920 Averill: C. C...................... July 9 October 471 1915 Baldwin, C. Kemble............... Aug. 9 October 471 1926 Barquist, Walter C............... NOV. 14 June 298 Barron,* Clarence Walker......... Oct. 2 November 511 1917 Beasley, Fred E.................... Aug. 31 October 471 1901 Belden, S. B....................... May 15 July 333 1927 Binney, Edwin, Jr.................. Dec. 29 February 96 1915 Bonsall, James Malcolm............ Feb. 12 June 284 1917 Boyle, John....................... July 12 December 561 1913 BradEn, Eugene B............. Jan. 29 March 157 1889 Bulkley, Frank.................... Mar. 25 May 240 1896 Callaghan, J. T., Jr............... Apr. 1 1892 Chalmers, George.................. Feb. 4 April 197 1898 Clark, Josiah H.................. May 7 July 333 1887 Copeland, F. K............. Nov. 10 December 561 1915 Cunningham, B. L11............... Dec. 6 August 294 1888 Dana, R. T........................ Aug. 20 December 559 1907 Dennis, Clifford G............... Dec. 28 March 1 1920 DeVenny, Thomas................ Feb. 13 April 197 1882 d'Invillier-, Edward V........... Jan. 4 March 157 1884 Duncan, M. M..................... Dec. 17 February 96 1924 Dyrssen, WaldemaR ............... Aug. 4 October 471 1906 Edmondson. H. W................ Dec. 21 February 1884 Emmerton, F. A.................. Oct. 9 June 298 1911 Eu, S. H............................ July 20 February 1917 Farrand, Ira W.................... Sept. 6 October 469 1900 Fell, E. Nelson...........•......... Mar. 25 May 231 1918 Fenton, Clarence M.............. October Junet 298 1908 Ferraris, Erminio................. Sept. 22 June 298 1914 Galloway. A. D. R............... December April 215 1924 Grant, A. W., Jr................... .4pr. 5 June 285 1917 Grant, Clifford G............... Jan. 26 January? 37 1918 Grant, Frank E.............. Jan. 14 September 417 1921 Gunderoth, C. J.................. Feb. 15 1897 Harms, Ernest..................... Aug. 12 November 512 1891 Hartrick, J. S..................... Feb. 9 June 285 1925 Hochschild, Berthold.............. Jan. 24 April 197 1917 Hutton, L. W...................... NOV. 3 January 37 1894 Jenning", S. J...................... NOV. 17 December 560 1925 Jones, J. Ravenscroft............... Jan. 29 March 157 1880 Jones, J. T......................... May 4 June 284

Jan 1, 1929

By George F. Becker

A Nere record of Emmons's professional career would very inadequately represent the man. That he was eminent mc know, and our successors will realize in due time; but they must depend upon us for knowledge of a singularly ~vholesome, modest, unselfish personality, and of a character that did honor to a profession in which trustworthiness is indispensable. Those members of the Institute who met Emmons are his friends, and I never knew .one of these who was not the better for that friendship. Emmons was born in Boston, Mar. 29, 1841, the son of Xathaniel H. and Elizabeth (Wales) Emmons, and was named Samuel Frankliri after an ancestor who was of the sarne family as Benjamin Franklin. He took the degrcc of Bachelor of Arts at Harvard in 1861, and soon afterwards went abroad to complete his education. From 1862 to 1864 he attended the courses at the fieole Impkriale des Mines at Paris, Elie de Beaumont arid Daubrke being among his professors. The year 1864-1865 he spent at Freiberg under Cotta and other famous teachers; after which he spent another year in traveling through Europe. Like many other renowned geologists, he approached his ultimate profession from its economic side, and was thus from the first imbued with a sense of high responsibility in the promulgation of scientific opinions or conclusions. With hypotheses which were interesting merely because they were ingenious or even plausible, he would have nothing to do. In 1867 he joined the Geological Exploration of the Fortieth Parallel at its organization under Clarence King, serving at first as a volunteer, but soon receiving a regular appointment. This expedition was the first one of purely geological character sent out by the United States government. As Emmons has shown in his admirable presidential address on " The Geology of Government Explorations," its work was founded on a com-

Jan 1, 1912

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

Separates of all the Technical Publications published in 1931 are available at Institute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the Transactions. Copies of these papers have been mailed to those members of the Institute who are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Institute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; K-Mining Administration; L-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Additional copies are sold at the rate of I cent per page; minimum charge, 25 cents. Metal Mining Tech-nical Publi- Title Author Meeting TRanb. cation Volume No. and Page* 411-A.43 Ventilation at the Portovelo Mines, J. P. Harmon New York. T31, 83 Ecuador (18) Feb., 1931 425-A.44 Use of Models for the Study of Mining P. B. Bucky New York, Problems (28) Feb., 1931 Milling and Concentration 375-B.32 Ball Mill Studies, I (53) A. W. Fahrenwald New York, H. E. Lee Feb.. 1931 401-B.33 Experimental Flotation of Oxidized H. S. Gieser New York. Silver Ores (9) Feb., 1931 410-B.34 Flotation of Minor Gold in Large-scale E. S. Leaver New York, Copper Concentrators (32) J. A. Woolf Feb., 1931 414-B.35 Effect of Particle Size on Flotation A. M. Gaudin New York, (23) J. 0. Groh Feb., 1931 H. B. Henderson 416-B.36 Ball Mill Studies, 11.—Thermal A. W. Fahrenwald New York. Determinations of Ball Mill Effi- G. W. Hammar Feb., 1931 ciency (13) H. E. Lee W. W. Staley Iron and Steel Division 38QC.59 Open-hearth Steel Process as a Prob- E. R. Jette New York, C31, 80, 111 Iem in Chemical Kinetics (34) Feb., 1931 381-C.60 Thermodynamic Study of the Phasial Yap, Chu-Phay New York. Equi1ibriain the System Iron-car- Feb., 1931 bon (26) 382-(3.61 Influence of Dissolved Carbide on the Yap, Chu-Phay New York, Equilibria of the System Iron-car- Feb., 1931 ban (19) 383-C.62 Research on Blast-furnace Slags. R. S. McCaffery New York, Three papers (88) Co-workers Feb., 1931 384-C.63 Statistical Analysis of Blast-furnace K. S. McCaffery New York, C31, 60, 70 Data (13) R. G. Stephenson Feb., 1931

Jan 1, 1931

By H. T. Kennedy, S. G. Dardaganian, J. L. Clanton

This paper presents equilibrium ratios measured on oil and gas samples taken from the Kelly-Snyder field at the reservoir temperature of 128°F. From these data smoothed curves were constructed for the reservoir fluid up to the bubble-point, 1,874 psia. A material balance calculation, based on the use of equilibrium ratios instead of the usual solubility and shrinkage meayr~rements is made on the field and compared to the con\.entional method. DETERMINATION OF EQUILIBRIUM RATIOS The equilibrium ratios, or K values were obtained by recombining separator samples of oil and gas taken when the reservoir was above its bubble point, and thus represented the reservoir fluid before any change had occurred due to the evolution of gas. The well sampled had a gas-oil ratio of 617 cu ft of high pressure sepalator gas per barrel of separator oil. and a bottom-hole temperature of 128°F. Samples were brought to equilibrium by agitating for 24 hours in a thermostat, maintained at the proper temperature within 0.2ºF, mercury being added when necessary to maintain the pressure constant. Samples of oil and gas were then taken by constant pressure displacement, and analyzed by low temperature frac-tionation. Equilibrium ratios were determined at 128°F and 500, 800, 1,000 and 1,400 psig. At the latter pressure, there were indications that the gas samples were contaminated with small quantities of oil, and only data taken at the first three pressures were included in Fig. I. This figure has been extended to higher and lower pressures by the use of the Fluor charts for 3,000 psi convergence pressure, on which the experimental points fit well. MATERIAL BALANCE EQUATIONS The possible errors involved in conventional material balance equations have been analyzed by Muskat1. Where the errors occur in field measurements, or in obtaining effective averages from variables such as gas-oil ratio and pressure, they will evidently be involved in any attempt to estimate the content of the reservoir. On the other hand, substantial errors may be introduced in conventional material balance calculations by: (1) the neglect of the amount of oil dissolved in gas at high pressures and temperatures in the reservoir, but which condenses under separator conditions; (2) the assumption that the separation of oil and gas in the reservoir may be duplicated by a differential liberation in the

ANDERSON, ALEXANDER, Captain, Royal Garrison Artillery. ANDERSON, GEORGE K., JR., Lieutenant, 30th Co., 3d Replacement Regiment. ARMSTEAD, H. H., Captain, Quartermaster Corps, U. S. N. A. ARMSTRONG, HAROLD KERR, Student Flight Officer, U. S. Naval Reserve Flying Corps, Dunwoody Naval Training Station, Minneapolis, Minn. BAKER, HARRY A., Captain, Co. M, 53d Pioneer Infantry. BASSETT, THOMAS E., Corporal, 340th. Field Artillery, Battery A, 89th Division, A. E. F. BATES, Wm.. T., 3d Reserve Officers' Training Camp. BAUMMGARTEN, K., 1st Lieutenant, 1st Corps School A. P. 0. 703. BAYLESS, G. E. S., Supply Dept., U. S. Submarine Base, New London, Conn. BENSEL, J. A., Major, U. S. R., Board of Control, War. Construction Activities, Norfolk, Va. BILLICK, DON C., Co. C, Ordnance. Supply School. BILLINGSLEY, PAUL, 1st Lieutenant, National Army, Statistics Branch,. General Staff. BLANDY, S. H. B., B. E. F.

Jan 8, 1918

By Richard B. Greenwalt, John M. Bertram, George E. Aiken

Agglomeration developments in the iron ore industry of North America over the past twenty years are closely related to shifting patterns in commercially acceptable ore grades and even the definition of iron ores. As early as WW II the rich Mesabi hematites were depleted, ending a 50-year era of direct shipping ores that included reserves of an estimated three billion tons. Decreasing ore grades and rising costs began to force the closing of many underground iron mines and processes were being developed to use domestic low-grade iron deposits. This resulted in the rapid development of iron ore beneficiation processes and signaled the coming trend toward concentration, sintering and pelletizing. Yet even today when agglomeration facilities are treating 90 % of the Mesabi Range product much remains to be done in keeping world-wide competitive forces in check and in ensuring the long- term utilization of these expansive ore supplies in an up-until-now captive U.S. market.

Jan 10, 1973

By A. T. Miesch, L. B. Riley

Distribution of minor elements in sandstone-type uranium deposits of the Colorado Plateau is being studied by the USGS on behalf of the A EC. A primary objective has been to provide basic data which could be useful in geo-chemical exploration for new deposits. The basic statistical measures — similar to those used in sedimentary petrology—are described. The underlying principle is that the frequency distributions fit or approach the log-normal form. Since 1952 the U. S. Geological Survey on behalf of the U. S. Atomic Energy Commission has conducted a study of the distribution of minor elements in sands tone-type uranium deposits of the Colorado Plateau. A primary objective in this study has been to provide basic data which could be useful in geo-chemical exploration for new deposits. Among the basic data considered important are estimates of the abundance and habit of each element in the ore and in the host rocks. It has been found that a few basic statistical techniques, and variations of these techniques, are useful in this type of study. Some of the basic techniques have been used to advantage by researchers in geochemistry and in other fields of geology, especially sedimentary petrology; others have been used to only a limited extent. Among the latter is the linear correlation coefficient, which has proved useful in assessing the element associations in a particular rock type without analysing individual mineral separates. In computing the basic statistical measures a scale has been used which is, in some ways, similar to the phi ($) scale used by sedimentary petrol-ogists in grain-size studies.' FREQUENCY DISTRIBUTIONS It has been recognized for some time that the results of analyses for a given minor element in a suite of samples of rocks or ores yield frequency distribution curves which are approximately normal when the curves are plotted on logarithmic or geometric scales. In other words, the analytical results give an approximate lognormal frequency distribution. A classical example is given by D. G. Krige2 in the study of the distribution of gold values from a mine on the Witwatersrand. Another example is shown in Fig. 1, the distribution of barium concentrations in samples of uranium ore from the Chinle formation. The geochemical data are analogous to grain-size data gathered by the sedimentary petrologist. Both types of data, after simple logarithmic transformations, may be treated by conventional statistical methods based on the normal distribution. This is not to say that other types of transformations may not serve equally well or better for particular element distributions.3 Spectrographers and other analysts are quite aware of the dependence of their precision on the concentration of the element present.4 For example, in the part per million range the variation may

Jan 1, 1961

CONTENTS PAGE FOGLER, M. F., and QUINN, E. J.-Scratch and Brinell Hardness of Severely Cold-rolled Metals. Discussed by H. S. Rawdon, Carl Benedicks, M. F. Fogler, A. L.Davis 1 GREEN, C. H. Eutectic Patterns in Metallic Alloys. Discussed by Carl Benedicks, Carle R. Hayward, G. E. Dalbey, George F. Comstock, C. H. Green. 3 ARCHER, ROBERT S., and JEFFRIES, ZAY.-New Developments in High-strength Aluminum Alloys. - Discussed by F. B. Coyle, M. F. Fogler, Zay. Jeffries, D. J. McAdam, Jr., Horace C. Knerr, Ernest Schweizer 6 FLICK, FULTON B.-Etching Aluminum and Its Alloys for Macroscopic and Microscopic Examination. Discussed by Samuel Daniels 22. MERICA, PAUL D., and WALTENBERG, R. G.-The Malleability of Nickel. Discussed by H. W. Gillett, Ancel St. John. L. W. McKeehan, A. L. Feild, A. L. Davis 23 ANDERSON, ROBERT J., and NORTON, JOHN T.-X-ray Evidence Versus the Amorphous-metal Hypothesis. Discussed by Zay Jeffries, Chu Phay Yap, Francis B. Foley, H. H. Lester, Edgar C. Bain, Ancel St. John, L. W. McKeehan, Carle R. Hayward, R. P: Heuer, Jerome Alexander, Carl Benedicks 26 COOK, MAURICE, and EVANS, ULICK R.-Recrystallization and Grain Growth in Soft Metals. Discussed by M. F. Fogler 36 POLUSHKIN, E. P.-Determination of Structural Composition of Alloys by a . Metallographic Planimeter. Discussed by H. S. Rawdon 36 BASSETT, WILLIAM H., and DAVIS, C. H.-Corrosion of Copper Alloys in Sea Water. Discussed by W. B. Price, W.. R. Webster, George A. Orrok, A. E. White, William H. Bassett, D. K. Crampton 38, Scratch and Brinell Hardness of Severely Cold-rolled Metals Discussion of the paper of M. F. FOGLER and E. J. QUINN, presented at the New York Meeting, February, 1925, and issued as Paper No. 1395-E with MINING AND METALLURGY, January, 1925. H. S. RAWDON, * Washington, D. C.-We had the privilege of looking over the data just given before they were published and we were not able to suggest any convincing reason for the differences that were secured

Jan 6, 1925

By S. A. Hovanessian

The method of characteristics which reduces the Buckley-Leverett mnlineur, partial differential equation to two first-order, linear differential equations is applied to the solution of a waterffood recovery problem for multiple lines of producing wells and one line of injection wells. The application of the method is described by a numerical example, and a brief theoretical background is given. From the results of this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple sets of producing wells. INTRODUCTION In this paper, the method of characteristics is applied to the solution of a waterflood recovery problem with multiple lines of producing wells and one line of injection wells. The application of the method to this type of recovery problem considerably simplifies the procedure of obtaining a numerical solution. It differs from the method described by Kern1 because it eliminates the need for integration in obtaining saturation fronts. In addition, the saturation history at any location within the field is obtained from a single diagram (time vs distance with saturation as a parameter)'. The paper includes a brief theory of the method of characteristics and its application to the solution of oil recovery problems. A numerical example is worked out, and the cumulative oil recovery-vs-time curve for a system with multiple sets of producing wells is obtained. This curve is then compared with the recovery curve of a system with only one set of producing wells. From this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple lines of producing wells. However, the recovery time is considerably longer for multiple sets of producing wells.

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By R. C. Neavel

One of the most important requirements to be met by any coal producer is delivery of size consists tailored to specific applications. Generally these specifications include a minimum as well as a maximum size limit. The customers of a major Indiana coal producer noticed that some shipments of sized coal contained a large proportion of undersize pieces. Also, in these shipments, the pieces which remained within the specified limits were cracked and, when handled, crumbled readily. The producer, certain that these shipments had been properly sized at the tipple, suspected that degradation had occurred in transit. The Indiana Geological Survey was requested to examine the coal from one of these shipments to attempt to determine the cause of breakage. Two basic facts about coal and coal seams led to the employment of petrographic techniques in this investigation. First, all coal seams consist of accumulations of diverse organic and inorganic constituents; and second, most coal breakage, either desirable or undesirable, can be attributed to the inherent weakness of some of these constituents or to poor adhesion between certain constituents. Analyses of degraded coal Sampling: Samples were secured from 2 stock piles of 2-by 4-inch coal in a dealer&apos;s yard. The coal in both piles had received the same treatment from mining to storage, although it had been mined and shipped on two different days. The size consist of one pile, however, appeared smaller than that of the other. The sample from the degraded pile is referred to as the slack sample, and the other is called the unslack sample. Size analyses: In order to determine the actual size consist, the samples were screened, with a minimum of rough handling, on square 2-inch, 1-inch, 1/2-inch, and 12-mesh screens. It is assumed that 100 percent of the 2-by 4-inch coal is retained on a 2-inch round screen at the tipple. Analyses of several loads at the tipple indicate that approximately 26 percent of the 2- by 4-inch coal, 100 percent of which was assumed held on a 2-inch round screen, passed through a 2-inch square screen. Twenty-six percent may be taken as the normal difference between round and square screens. Results of the analyses of stockpile coal are shown in Table 1. Cumulative percent versus size are plotted on a Rosin-Rammler chart as Figure 1. Both samples approximately follow normal size distribution; this indicates that breakage is not size preferential and also that the samples are representative of the stockpiles. Although both samples exhibit the same general size distribution, the median size of the slack sample is considerably smaller than that of the unslack sample. Fifty-five percent of the unslack sample was undersize (29 percent greater than the normal 26 percent difference), and 83 percent of the slack sample was undersize (57 percent greater than the normal 26 percent difference). Both piles contained a greater percentage than normal of undersize coal; this indicates that they were both affected by degradation, but to a different degree. Bedding-plane analyses: Coal, because of its laminated nature, will break preferentially along bedding planes, especially where adjacent constituents are poorly cemented to each other. Subsequent breakage perpendicular to the

Jan 1, 1961

By N. A. Gokcen, S. Fujishiro

The dissociation pressure of Cr3C2 has been measured in the range of 1908" to 2237°K by means of graphite Knudsen effusion cells. It has been found that Cr3C2 vaporizes according to the following reaction: 1/3 Cr3C2 (s or 1) = 2/3 C (graph.) + Cr (g). The equilibrizcm pressure, P, of Cr (g) is found to be log Ps=- - (21,194/T) + 6.525 over solid Cr3C2 and estimated as log P, = - (19,535/T) + 5.76 over liquid Cr3C2. CARBIDES of chromium are of great importance in alloy steels and cemented carbides. The published data on their therm odynamic properties at high temperatures, however, are meager. The heat capacity and change in entropy of Cr3C2 were determined calorimetrically by Kelley and Moore1 in the range of approximately 50" to 300°K, and by Oriani and Murphy2 from 297" to 1188°K. The standard entropy of Cr3C2at 298.15°K, obtained by Kelley.7 was later confirmed by DeSorbo.4 Equilibrium in the reaction was investigated by Boericke.5 A recent tabular summary

Jan 1, 1962

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10&apos; nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described&apos; that comes close to being in the proper range.

Jan 1, 1954