Search Documents

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

Following the suggestion of Engineering Council and at the direction of, the President, representatives from each of the Federal Government bureaus interested in map-making were called into a conference for the purpose of coordinating all of the Government's map-making activities. This conference has now reported back to the President the results of its findings, which indicate that Engineering Council's recommendation in this matter was well founded. While the conference report states that its members were of the opinion that little duplication of effort existed, it recommends the formation of a permanent Board of Surveys and Maps. An extended review of the map-making activities, which is given as an appendix to the report, indicates that this recommendation is a logical step. The conference recommendations concerning this Board of Surveys and Maps are as follows: (1) the Board is to he com-posed of representatives of mapping bureaus to be assisted by outside engineering organizations, which have been named above; (2) the estab-lishment of an information office in one of the Government bureaus, preferably the Geological Survey, which is to be under the supervision of the Board and is to be a mapping information clearing house for the Government and outside engineering organizations; (3) copyright laws are to be so changed that copies of all. maps made in the United States and with Governmental authority, will go to the central information office; (4) the Government departments are to receive orders to cooperate, with the Board; (5) future topographic maps of all kinds are to conform with specifications for the standard topographic map; (6) the U. S. Coast and Geodetic Survey to have supervision of final adjustment of all important control data under specifications approved by Board of Surveys and Maps; (7) surveys in the form of maps and publications are to be issued as soon as possible after field work has been completed; (8) program of the Interdepartmental Committee on Aerial Surveying was approved. Outside technical and scientific organizations that are called in for consultation are to operate in an advisory capacity only, responsibility for action on Governmental work is. to rest solely with the Governmental agencies.

Jan 12, 1919

Book Review MANAGEMENT AND MEN. By Meyer Bloomfield, Boston. The Century Co., New York, 1919, pp. 584, H.X. 5 1/2. $3.50. This hook is an exposition of English efforts to solve the problem of labor unrest in England. The first six chapters are reprinted from articles published in the Satur-day Evening Post, for whom the author went to England to study the problem at first hand. These articles deal with housing, increased production, eliminating the internal friction in the industrial machine and a chapter each devoted to the view-point of employer and employee. These chapters are written in the easily readable magazine style and give a complete general survey of the particular solution being tried. Perhaps their greatest., certainly not their least, worth lies in the fact that they form a vehicle for unusually voluminous appendices containing in full the famous Whitley Reports which are the basis of the new movement, together with various reports, which, except for this publication, would be largely inaccessible to those inter-ested in this country. The Whitley scheme considers each industry a unit and proposes to establish therein a Joint Standing Industrial Council composed of representatives of employers and employees to consider appropriate matters affecting the industry at large. There is to be a District Council for each industry which will, as its name implies, deal with the clatters pertaining to that interest in. the particular district. The third and last body in this scheme of Industrial Parliament is the Works Committee, which is com-posed of representatives of the management and of the workers employed in particu-lar plants or mines to act in close cooperation With the district quid national machinery. The Whitley or similar schemes have been tried in many communities in England and the book contains interesting comments on the result obtained, it being notable that most of the objections conic from plants which have not tried the scheme. Meyer Bloomfield, the author; is the specialist in industrial personnel problems who organized the industrial service activities of the United States Shipping Board, Emergency Fleet Corporation. P. E. B.

Jan 10, 1919

THE distinction btween price reduction as a re-sult of lowering of production cost and price re-duction through unrestricted competition cannot be made too clear, because they are often interwoven in actual experience. Take the whole population of a town whose principal industry is shoe manufacturing as a concrete example. If the manufacturer is able to cut his price per pair in half because he has found out how to make a pair at half the cost, he will com-monly let a number of his men go, because reduction in production cost usually results from substituting cheap mechanical energy for expensive human energy. These people will normally find other employment. The workmen who remain employed usually earn more in dollars than they did before, and in spending it give employment where there was less before. Mining companies that initiate considerable enter-prises in foreign lands where the economic level is low, and where most of the people are busily but in-efficiently engaged in raising enough food to support themselves and their families, often find themselves confronted with an acute labor problem. If any con-siderable number of workers leave the land to work in and about the mines, those left on the land cannot raise enough food to keep them all unless they are taught better methods of agriculture and provided with equipment that will enable them to produce more with less expenditure of effort. Add to this the fact that managers commonly find that the "natives," as our British cousins designate them, usually need more food and a better balanced diet than they have been accustomed to in order to show anything above the lowest order of efficiency in industrial work,. and it is clear that to make a new industry possible in what may be termed an economic province involves increas-ing the productivity, not only of those who are em-ployed in it, but of the whole social group. It has already been pointed out that the employ-ment of large numbers of men in automobile manu-facture is only possible because the others have in-creased their productivity enough to turn out every-thing else that is needed without the help of the auto-mobile workers.

Jan 7, 1928

By H. W. Camp

ALTHOUGH the situation in the oil industry during the past year has. not been conducive to large expenditures for development and research, there is little indication that such expenditures have been curtailed. While few outstanding achievements have been reported, considerable progress has been made in the development of new products and the adaptation of petroleum derivatives to new uses. The most important question facing the refiner today is the anti-knock quality of his gasoline. This year has seen the widespread adoption of the term "octane number" as a measure for anti-knock values, and in the latter months of the year the public has been made acutely aware of this condition through competitive advertising. Gaso-line is no longer priced on volatility and gravity alone, but on octane number as well; and premiums are being paid for material of relatively high octane rating. The situation has grown more and more competitive and has forced refiners continually to raise the octane rating of their regular and com-petitive grades, and at this writing the same situation exists for premium grades which have possessed relatively high anti-knock properties for some time. Straight-run gasoline produced from paraffin-base or semiparaffin-base crudes has an inherently low anti-knock value, and in order to convert this material to a higher quality it has been found necessary to crack an increasing percentage of the crude oil charge. By completely cracking the heavier portions of the crude, and blending back with the straight-run gasoline, it has been possible to produce an average of 63 to 65 octane number gasoline' on average Mid-Continent crude. This operation carried to the fullest extent does not suffice, however, and the recent and rapid development of the so-called "re-forming unit," has resulted. The straight-run gasoline fraction is cut into two parts: a light, low boiling point gasoline; and a heavy gasoline or naphtha. The latter containing the low anti-knock portions of the gasoline, is sent through a re-forming unit and subjected either to high temperature ,or pressure, or both, which materially increases its octane number. On average Mid-Continent the blend of low boiling point straight-run,

Jan 1, 1932

By John B. Myers

VERMICULITE is a name used to describe micaceous material that exfoliates when heated. It is hydrated magnesium-aluminum-iron silicate. The chemical composition, color, physical appearance, and degree of exfoliation vary. COMPOSITION, PROPERTIES, AND ORIGIN Vermiculite has the characteristic micaceous structure of basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. Hardness is 1.5; specific gravity, 2.2-2.7; luster pearly to greasy; colors, amber, bronze, reddish brown, dark green, and black. Feel is soapy, particularly when wet. When heated it exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin veamiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted into steam. Warping of the unit layers may also contribute to the expansion. The increase in bulk volume of commercially prepared material is 8 to 12 times but individual flakes may increase in size more than this. Pure vermiculite is a distinct mineral and has the structural formula (OH), (Mg,Fe)3 (Si,Al,Fe)4 010.4H20. It rarely occurs in this pure form, but generally as a mixed mineral of varying structure. One explanation is that the mixed material is composed of unit layers of inter-stratified pure vermiculite and biotite. The essential difference between the two is that unit cell structure of vermiculite contains a layer of water molecules whereas the biotite cell contains potassium instead of the water. The water content of the mixed vermiculite is less than that of pure vermiculite but more than that of biotite. Pure biotite does not expand when heated. If the proportion of biotite layers in a vermiculite is too high it will adversely affect the degree of exfoliation. Within a given deposit, the great mass of material may approach a definite com-position with local areas of greater biotite content. It is not uncommon to find also small pockets of pure biotite but these are generally segre-

Jan 1, 1949

By Joseph L. Gillson

IT is a somewhat curious circumstance that the newest of the Institute's several awards should be conferred in the oldest of our several professional fields—for there is little question that geology and mining have antedated metallurgy and petroleum. Perhaps so did geophysics. After all, one geophysical instrument, the magnetic compass, has been successfully employed for many centuries. Young in years the Jackling Award may be, but in distinction—whether in terms of the title it bears or in terms of the first three medalists (Reno Sales, E. D. Gardner, and the late Father MaceIwane)—the Jackling Award is already one of the ranking awards of the Institute. The name of the 1957 medalist will bring added luster to an already illustrious roll. J. L. Gillson was born and brought up in Evan-ston, Ill., in an area characterized by singularly flat and uninspiring topography, and devoid of ore deposits and even of bedrock—a most unlikely environment from which to expect a future Jackling medalist to emerge! On graduating from high school he enrolled as a chemistry major at Northwestern University. At the end of his frkshman year his scholastic prowess had won him a prize of two chemistry books. But these went unread, for about this time he came under the spell of U. S. Grant, that distinguished and enthusiastic geologist who for many years was head of Northwestern's geology department. From thence forward Joe was a dedicated geologist. After a Navy interlude in World War I, he went to MIT for graduate work, substituted for the late Professor Palache for one year at Harvard in mineralogy, received his doctorate at MIT and stayed on as a meniber of the MIT faculty, where the geology department was headed by that great dean of all economic geologists, Waldemar Lindgren. In 1926 Joe spent a summer looking into barite deposits for the du Pont Co., and since 1928 he has been du Pont's chief geologist. Do men who lead such active lives in our exploration organizations generally have permission to publish their observations? Do they generally find time to publish, even if they have permission? Alas, no. But in Joe Gillson's case, yes. His bibliography runs to well over two score papers, including one of the very first papers in this country on the applications of petrography to problems of Portland cement. He has written on such topics as the origin of talc and the genesis of ilmenite, fluorspar, and alkaline rocks. Each year for a number of years his annual reviews of industrial minerals in the Mining Congress Journal have been eagerly awaited. - Do men who do so much to advance their science have anything left to give to the advancement of their profession? In Joe Gillson's case, yes. He has been a vice president of the Mineralogical Society of America and has been active in the councils of the Society of Economic Geology, particularly in their research programs. This year he is president of the American Geological Institute, currently perhaps the most challenging post to which a geologist may be elected. His contributions to AIME scarcely need documentation, so I shall mention only three—his chairmanship of the Committee on Democratization of the Institute, a committee whose work and recommendations brought a new and hopeful leaven to AIME at a time when this was sorely needed; his chairmanship, a few years ago, of the Industrial Minerals Division; and his current place on the Board of Directors as Vice President of the Institute. Such' a catalogue of contributions and achievement, even as condensed as I have had to make it, certainly merits the Jackling Award. Yet, implicit although not often expressed in the conferring of most awards is the hope that besides recognizing a distinguished career, it will provide stimulus for further effort. In the present instance, such an expectation is already well on the way to fulfillment. Only recently Joe Gillson has undertaken the editorship of a new and greatly revised edition of the Institute's Seeley Mudd volume, Industrial Minerals and Rocks. And so, Mr. Chairman, it is with pleasure and enthusiasm that I present Dr. J. L. Gillson for the 1957 Jackling Award.

Jan 1, 1958

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By A. H. Tousley, C. L. Vickers

The author presents a history of the development of the Port of Long Beach from its beginning in 1905 to the present construction of a new bulk loading facility. In describing this new facility, emphasis is placed on such aspects as rail car and truck handling, gravity yard, rotary car dumping, bottom dumping, car dumping equipment, feeding and conveying, ship-loader-stockpiler, stockpiling and reclaim, dust control, and construction problems. Development of the Port of Long Beach, Calif. (see Fig. I), began in 1905. In that year private Long Beach interests acquired 800 acres of marshland in the Inner Harbor area and initiated a program of channel dredging and land reclamation. Efforts to establish a municipal port began a short time later and culminated in the opening of Pier 1 in 1911. An event of even greater significance to the port future also occurred in 1911. This was the tideland grant enactment by the state legislature that conveyed to the city of Long Beach all of the state&apos;s rights in the tidelands located within the city boundaries. The grant stipulated that all revenue produced from the tidelands be used for the development of navigation, commerce, and fisheries. During the next 15 years up to 1926, the port&apos;s commercial growth was steady, although relatively slow. During this period, several fundamental steps in the development of a major harbor were accomplished. These included the creation of the Board of Harbor Commissioners in 1917, the dredging of the Inner Harbor and entrance channel to accommodate deep draft vessels, and the correction of a serious silting problem through construction of the Los Angeles River Flood Control Channel. These efforts bore fruit during the ensuing 10 years in the establishment of more than $30,000,000 worth of industrial plants and private marine terminals in the Inner Harbor. Commerce over municipal wharves also increased more rapidly, and it became necessary to start the development of the harbor in a seaward direction. In 1936, oil was discovered in the harbor area, and the first Harbor Dept. well was brought in 2 years later. It soon became evident that the city of Long Beach would receive substantial revenue that, under the terms of the state grant of 1911, must be used in the development of the port. It was further realized that to properly guide and coordinate such development, a long range comprehensive plan was essential. The Board of Harbor Commissions contracted with G. F. Nicholson and J. F. Collins, consulting engineers, for the preparation of such a report that was completed in 1940. The Nicholson-Collins report proposed the development of an East Basin, between the entrance channel and the Los Angeles River, and a West Basin in the area now occupied by the Long Beach Naval Shipyard. Twenty full-size berths were to be provided in the East Basin and more than fifty berths in the West Basin. The report recommended extensive modern terminal facilities for handling waterborne cargo. Attention was given to improvement of the street and highway system to give better vehicular access and to avoid congestion within the port. To a large extent the recommendations of the Nicholson-Collins report were followed in the subsequent development of the East Basin. This development was greatly accelerated by World War 11, with its need for increased oil production and additional shipping facilities. The wartime and immediate postwar construction was largely concentrated on Pier A, with the development of Piers B, C and D following in more recent years. An important factor in the planning of these piers was their dual function as oil drilling sites and cargo piers. The Navy&apos;s acquisition of the West Basin area made it necessary to depart from the Nicholson-Collins plan and find other areas for future expansion. At the present time only one Inner Harbor Port-owned area having protected deep water frontage remains undeveloped. This is the property fronting on Channel 2 in the Inner Harbor acquired in December 1957, from Pacific Dock and Terminal Co. The growth of the port has been in a southerly direction since the construction of the Long Beach Naval Shipyard in the West Basin area. Recent extension of Piers F, G and J into the ocean follows typical port construction methods developed during the expansion of the Middle Harbor during the last 20 years.

Jan 1, 1963

By R. D. Russell, R. M. Farquhar

SOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing iso-topic tracers to obtain information about the geological history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium Occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts comparable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample. It is this unique property of lead that serves as a means of tracing the history of a lead sample in terms of its contacts with the radioactive elements. If lead from a lead mineral has been analyzed with a mass spectrometer, the measured isotope ratios are determined entirely by the isotope ratios of primeval lead, which are identical for all minerals, and by the particular history of the sample. It follows that for samples from any particular geological area, observed differences in the isotopic composition are enough to distinguish different geological histories. An illustration of the qualitative application of this statement is given in Table I by analyses of some galenas from the western Cordillera. Samples from deposits in Pre-Cambrian sediments have very different lead isotope ratios from those of the ores in the Paleozoic sediments. Although the two types are associated closely geographically, it is apparent that they have had quite different histories and have probably been emplaced at quite different times, as the ideas outlined in the following section suggest. Even when applied quantitatively, a lead isotope analysis can never indicate a unique history of any lead sample. However, it greatly restricts the choices available and combined with other geological and geochemical data can lead to a much better understanding of the genesis of lead ores. General Character of Lead Isotope Variations: Early isotopic analyses of common leads by Nierl showed that geologically younger leads were generally richer in isotopes of masses 206, 207, and 208, with respect to that of mass 204. This regularity of measured lead isotope ratios can be easily observed by plotting each of the ratios Pb207/Pbm and Pb205/ Pb204 against the ratio Pb206/Pb204. In both graphs the points lie scattered closely about a well defined mean curve. It was immediately supposed that this regularity resulted from the growth of all leads from a common primeval lead present at some time, To, early in the earth&apos;s history. Lead in the outer part of the earth would become continually enriched in the radiogenic isotopes as a result of the uranium and thorium intimately associated with it. The subsequent extraction of some of this lead and formation of a lead mineral free of the radioactive parents provide samples of lead existing in the earth at the time of mineralization, T. Younger leads in general will be richer in the radiogenic isotopes because they have been associated with uranium and thorium for a longer time. Then lead ratios would be given by the formulae: (Pb206/Pb204)YTPb^/Pb204) +f "(u201) kdt T (Pb207Pb204)r = (Pb208/Pb204)T0 + J (U295/Pb204) k&apos; dt T (Pb208/Pb204) t = (Pb208Pb204 + J (Th204) A." dt [1] where A, A&apos;, and A" are the decay constants of U238, U285 and Th232. Summaries of measurements of radioactivity of surface rocks, such as given by Faul,2 are of limited

Jan 1, 1958

By R. E. Miner, J. K. Jackson, T. L. Wilson

A study has been made of the transformation kintetics and morphology in gas-quenched Fe-5 pct Ni alloys. Massive ferrite or nlurtensite was found to form at temperatures in agreement with earlier results. Surface Preparation appeared to have the greatest effect in determining the type of transformation Product formed. Grain size change, subgrain morphology, and dislocation densities of massive ferrite were essen-tinlly invariant functions of cooling rate. The mar-tens~tic structures were typical of transformation in austenite grains of the order of the sample thickness. BY introducing the idea of a massive transformation in dilute iron-base alloys, Gilbert and Owen in 1962 served to stimulate a closer inspection of phase transformations in ferrous systems.&apos; A wealth of literature has followed concerned with the morphology,2-5 transformation mode,2&apos;3&apos;6-8 and thermodynamics of transformations.2,5,9 interesting controversies have resulted from the experimental observations; closer attention has been paid to the definition of massive transformations and still to be resolved is the Ms temperature of pure iron. The purpose of this note is to report some observations made in a detailed kinetic and metallographic examination of the transformations that occur in gas quenched Fe-5 pct Ni. The results are pertinent to the Ms extrapolations that have been made for pure iron and the observed substructure of massively transformed alloys. PROCEDURE The material used in this investigation was cast as a 5 lb vacuum induction melted, carbon deoxidized heat. The ingot was hot worked to a strip 0.10 in. thick, decarburized, and cold rolled to final thickness. Specimens were punched to sample shape and decarburized in wet hydrogen at 600°C. The chemistry of test specimens is indicated in Table I. Samples 1 by $ in., by thickness were resistance heated and rapidly cooled in an apparatus as illustrated in Fig. 1. Similar helium quenching apparatuses have been described previously;2,6&apos;10 the distinguishing feature of this apparatus is the nozzle geometry. Twin nozzles with three convergent-divergent, sonic ports were mounted perpendicular to the specimen for quenching purposes. The specimen temperature was monitored with an intrinsic 3 mil chromel-alumel thermocouple spot welded to the specimen and con- nected to an oscilloscope. A single switch stopped the current flow through the specimen, opened a gas flow solenoid valve, and initiated an oscilloscope sweep. Cooling rates were read directly from a photograph of the oscilloscope trace and the quenching rates quoted later were made at a point immediately prior to transformation on the trace. All quenching studies were conducted either under a vacuum of 10"-5 torr or a helium atmosphere. The sample geometry was chosen large enough to permit optical and electron microscopy to be performed on samples. The samples were electropolished for both types of examination in a perchloric-acetic solution. Electron microscopy was conducted on a HU 11A microscope operated at 100 kv. Dislocation densities were determined at the same general operating reflection (110) on foils thick enough to produce Kikuchi patterns. RESULTS AND DISCUSSION Transformation Temperature Observations and OD-tical Microscopy. The quenching results of this study are illustrated in Fig. -2(a). Samples which were treated in the as-decarburized condition transformed in a manner similar to that reported previously—a decrease in transformation temperature occurred as the quenching rate increased until a plateau region was reached. Within the scatter of the results obtained here, there was no break in the transformation temperature-quenching rate plot. This suggests no change in transformation mode. Further metallographic examination confirmed this observation. A martensitic transformation was obtained for similarly treated samples except that the surface was first electropolished. The Ms temperature was approximately 85°C below the plateau determined for the unpolished samples and cooling rates as slow as 2000°C per sec were adequate for producing marten-site. The transformation temperatures are in gen- / STRIP SAMPLE / COPPER I SAX/-/}&apos; / CONNECTOR-----A f, SON|C poRTS AC LEADS 3j ]j"I rofe[ \ Mf/yinK/iKj&apos;&apos;^ THERMOCOUPLE X-(^—iie"s*c? &apos; LEADS 1 INCH Fig. 1-—Schematic scction of gas quenching apparatus

Jan 1, 1970

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES &apos;J. 1. IToffmon and B. T. Scribrer: I. Research h&apos;atl. Bur. Standards, 1935, "01. 15, p. 205. &apos;W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. &apos;D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. &apos;K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. &apos;W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."&apos; Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.&apos; Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

By Steve H. Carpenter, Henry E. Otto

The explosive welding of metals is dependent upon the production of a jetting action caused by the collapsing of one metal plate against another. Successful welds are generally accomplished if the yield strength of the metals is in the range of 10,000 to 90,000 psi and the sonic velocity of the metal is greater than the detonation velocity of the explosive if direct contact explosive is being used.&apos; Should the detonation velocity exceed the velocity of sound in the metal it may still be possible to obtain the jetting action and a good weld. However, in most cases where a high detonation velocity is used complications arise because of reflected shock waves which tear the bond apart as fast as it is put together.&apos; Explosive welding of lead presents several problems since its yield strength and sound velocity are very low. Various values have been published3-5 for the velocity of sound in lead ranging from 2000~ to 23004 m per sec. Most of the high-order explosives have detonation velocities on the order of 6000 to 8000 m per sec, which precludes their use. The dynamites have a lower detonation velocity of around 2800 m per sec which is still somewhat too high. Lower-order explosives such as ammonium nitrate (1070 m per sec) must be used to weld lead in the as-received condition if the explosives are used in direct contact. Rather than use low-order explo&apos;sives it was decided to alter the sonic velocity of the lead. The sonic velocity is directly related to the modulus of the material according to the following expression: Fig 1—Interface of explosive weld of lead to steel. Lead is on top As-polished Magnification 75 times as well as the yield strength. Bolling et al. 6 show that the shear modulus of lead single crystals increases from about 0.72 X1011 dynes per sq cm at 300°K to about 0.98 X1011 dynes per sq cm at 0°K, an increase of approximately 3 5 pct. This gives an increase in the sonic velocity of around 700 m per sec. Hence, the sonic velocity of lead at cryogenic temperatures is approximately equivalent to the detonation velocity of the low-order dynamites. We have obtained high-quality lead to steel explosive welds using a 40 pct dynamite in direct contact with the lead. Prior to detonation the lead was chilled with liquid nitrogen (78°K) to increase the strength and sonic velocity. Welds were made while the lead was cold. Specimen sizes were 3 by 6 in. A preset angle of 5 deg with a 0.10-in. standoff at the base was the geometrical setup used. The amount of explosive used for optimum welding of an 1/8 -in. -thick lead sheet to a steel plate was found to be 7 g per sq in. A PETN sheet explosive line wave generator was used to insure a linear detonation front through the dynamite. A photomicrograph of a lead-steel weld is shown in Fig. 1. The typical wave effect that constitutes a good explosive weld is present. When tested in shear, the weld failed in the lead, indicating that the bond is stronger than the lead base metal. Higher-order explosives were also tried without success. We believe this indicates the importance of matching the detonation velocity and the sonic velocity for successful explosive welding. Note Added in Proof. High quality explosive welds of lead to steel have recently been obtained at ambient temperature using a low velocity (1000 M per sec) free running dynamite. The weld interface obtained is comparable to Fig. 1. &apos;S. H. Carpenter, R. H. Wittman, and R. J. Carlson: Proceedings of the First International Conference of the Center for High Energy Forming, Syracuse University Press, syracu.se, N. Y., in press. &apos;A. HI Holtzman and G. R. Cowan: Welding Risearch. Council Bull., No. 104, April, 1965. &apos;Metals Handbook, 8 ed., p. 1062, Metals Park, Ohlo. &apos;J. M. Walsh, M. H. Rice, R. G. McQueen, and F. L. Yarger: Phys. Rev., 1957, vol. 108, pp. 196-216; &apos;L. V. Al&apos;tshuler, K. K. Krupnikov, B. N. Ledener, V. I. Zuchikhin,

Jan 1, 1968

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

By R. M. Genevray, M. B. Bever, E. J. Suoninen

THE martensitic transformation in the ß-phase of the Cu-Zn system has been the subject of several investigations. The transformation is known to be reversible and to be affected by stress. Its temperature range has been determined as a function of composition. In the investigation reported here, the effect of tensile stresses on the transformation was investigated quantitatively. Some information was also obtained on the thermoelastic behavior of the martensite formed in the first stages of the transformation. Most of the experiments were done with alloy E of an earlier investigation;&apos; this alloy analyzed 60.49 pct Cu and 39.51 pet Zn by weight. The methods of shaping and heat treatment were also essentially the same as those previously used. The stress was applied to the specimen immersed in a cooling liquid. The transformation was followed by measuring the electrical resistance with a Kelvin bridge and the elongation with a cathetometer. Fig. 1 shows the M, temperature as a function of stress. Resistance and strain measurements gave essentially identical values. The results suggest a roughly linear relation between M. and in the range investigated, up to 12 kg s mm". At higher stresses, plastic deformation begins to interfere seriously with this relationship. The increase of M, with stress is consistent with published work on the effect of stress on the martensitic transformation. The slope of the curve, 4°C per kg mm ", is of the same order of magnitude as the corresponding value calculated for steel.&apos; Fig. 1 also shows the difference, AM, between the temperature of 50 pct transformation on cooling, as measured by changes in length, and that of 50 pct reverse transformation on heating. This difference, which may be considered a measure of the hysteresis, increases with stress; the decrease at highest stresses is probably associated with plastic deformation. Preliminary work using only resistance measurements was done with an alloy containing 60.15 pct Cu and 39.79 pct Zn by weight. The results indicated higher values o-F M, in agreement with the known variation of M. with composition.&apos; The effect of stress on M, (2°C per kg mm-&apos;) was of the same order of magnitude as that shown in Fig. 1 for composition E. An increase in hysteresis with stress was also found. The following experiment was made in order to investigate a partially transformed structure. A specimen of alloy E was cooled to — 85°C under a stress of 4.7 kg mm-&apos;. Under these conditions, the martensitic transformation started but did not go to completion. The stress was then released and the specimen cooled to — 105°C. Fig. 2 shows the measured elongation c. The first change in the slope of the curve indicates the beginning of the transformation under stress. Removing the load at —85°C caused a decrease in length to the value corresponding to the elastic elongation of the parent phase resulting from the applied stress. Hence, the marten-site formed in the first part of the experiment apparently disappears completely and without hysteresis upon the release of the stress. The increase in length on further cooling indicates renewed formation of martensite. These conclusions are consistent with the concept of "thermoelastic" martensite," which has been confirmed by test." Acknowledgments The authors are greatly indebted to Professor M. Cohen for his advice and encouragement. They also thank F. Paxton for assistance. Thanks are due the American Brass Co. which supplied the alloys. References E. Kaminsky and G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1936) 6, p. 984. A. B. Greninger and V. G. Mooradian: Trans. AIME (1938) 128, p. 337. "J. E. Reynolds, Jr. and M. B. Bever: Trans. AIME (1952) 194, p. 1065; Journal of Metals (October 1952). &apos;A. L. Titchener and M. B. Bever: Trai~s. AIME (1954) 200, p. 303; Journal of Metals (February 1954). " 3. A. Kulin, M. Cohen, and B. L. Averbach: Trans. AIME (1952) 194. p. 661; Journal of Metals (June 1952). "J. K. Pate1 and M. Cohen: Acta Metallurgica (1953) 1, p. 531. &apos;C. Crussard: Comptes Rendus (1953) 237, p. 1709. &apos; G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1948) 18, p. 999. G. V. Kurdjumov and L. G. Khandros: Dokl Akad. Nouk. SSSR (1949) 66. p. 211.

Jan 1, 1957

By G. G. Gunther, C. L. Boeke

DISCUSSION I. M. Symonds, (Cia. Minera de Penoles, Monterrey, N. L., Mexico)—Messrs. Boeke and Gunther have written most interesting papers describing their zinc de-leading operations. Mr. Gunther was kind enough to show me his operation last fall. Aside from the excellent results, I was most impressed by the ease of control. I had expected a difficult operation requiring careful control and supervision, but found one requiring little attention. The only disappointing fact of the separation is the poor copper recovery in the concentrate of the delead-ing float. The final zinc concentrate still has about 3 pct chalcopyrite, assuming the copper is chalcopyrite, and adversely affects the zinc grade. If the copper mineral is free, the poor recovery is probably due to the high cyanide concentration. Fortunately, about 75 pct of the copper is recovered before the pulp goes to the zinc circuit. Mr. Gunther&apos;s remarks about proper cyanide to zinc sulphate ratios cannot be overemphasized. Although our experience has been confined mostly to the conventional lead-zinc separation, we have found these ratios most important, and more important in the mill than in the laboratory. The laboratory appears to give optimum results over a wider range of reagent control than the mill, especially in regard to the effect of cyanide. In handling relatively high grade ores in the mill we usually find that ratios of cyanide to zinc sulphate of 1 to 10 or 20 or higher work best. Where there is a substantial amount of chalcopyrite present it has been noted that cyanide in the range of 0.02 to 0.10 lb per ton of ore is often beneficial in zinc rejection and possibly in copper recovery in the lead concentrate, while larger amounts, say 0.20 to 0.25 lb per ton, will float more zinc and cause a serious rejection of chalcopyrite. On an ore with 15 to 20 pct zinc content we have had to use 0.8 to 1.2 pounds of zinc sulphate per ton of ore with the above cyanide to obtain optimum results. Some time ago we made a laboratory study following Parral and Santa Barbara practice on an ore which had never a very satisfactory rejection of zinc in the lead concentrate. The results were not encouraging and a mill test was not run. Since then the study has been reopened using in the laboratory fresh zinc concentrate from the mill instead of one made in the laboratory. A reasonably clean lead float from the zinc concentrate was obtained. It has been checked several times and each time the zinc concentrate made in the mill responds and the one made in the labora-

Jan 1, 1953

By G. G. Gunther, C. L. Boeke

DISCUSSION I. M. Symonds, (Cia. Minera de Penoles, Monterrey, N. L., Mexico)—Messrs. Boeke and Gunther have written most interesting papers describing their zinc de-leading operations. Mr. Gunther was kind enough to show me his operation last fall. Aside from the excellent results, I was most impressed by the ease of control. I had expected a difficult operation requiring careful control and supervision, but found one requiring little attention. The only disappointing fact of the separation is the poor copper recovery in the concentrate of the delead-ing float. The final zinc concentrate still has about 3 pct chalcopyrite, assuming the copper is chalcopyrite, and adversely affects the zinc grade. If the copper mineral is free, the poor recovery is probably due to the high cyanide concentration. Fortunately, about 75 pct of the copper is recovered before the pulp goes to the zinc circuit. Mr. Gunther&apos;s remarks about proper cyanide to zinc sulphate ratios cannot be overemphasized. Although our experience has been confined mostly to the conventional lead-zinc separation, we have found these ratios most important, and more important in the mill than in the laboratory. The laboratory appears to give optimum results over a wider range of reagent control than the mill, especially in regard to the effect of cyanide. In handling relatively high grade ores in the mill we usually find that ratios of cyanide to zinc sulphate of 1 to 10 or 20 or higher work best. Where there is a substantial amount of chalcopyrite present it has been noted that cyanide in the range of 0.02 to 0.10 lb per ton of ore is often beneficial in zinc rejection and possibly in copper recovery in the lead concentrate, while larger amounts, say 0.20 to 0.25 lb per ton, will float more zinc and cause a serious rejection of chalcopyrite. On an ore with 15 to 20 pct zinc content we have had to use 0.8 to 1.2 pounds of zinc sulphate per ton of ore with the above cyanide to obtain optimum results. Some time ago we made a laboratory study following Parral and Santa Barbara practice on an ore which had never a very satisfactory rejection of zinc in the lead concentrate. The results were not encouraging and a mill test was not run. Since then the study has been reopened using in the laboratory fresh zinc concentrate from the mill instead of one made in the laboratory. A reasonably clean lead float from the zinc concentrate was obtained. It has been checked several times and each time the zinc concentrate made in the mill responds and the one made in the labora-

Jan 1, 1953