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By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By G. Bassi

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

Jan 1, 1953

By G. L. Kehl, Emilo Jaraiz F., J. S. Brett

The transformation of eutectoid beryllium bronze has been quantitatively investigated at 550° and 592°C, the temperature region where the products of p decomposition are a fine lamellar eutectoid and a coarse lamellar aggregate which replaces the fine eutectoid with prolonged annealing. Metallographic evidence indicates that the coarse lamellar aggregate forms preferentially in the most densely lamellated regions of the fine eutectoid and favors the hypothesis that the development of the coarse lamellar aggregate in the fine eutectoid is due to the occurence of a cellular segregation reaction. WHEN eutectoid beryllium bronze (Cu-94 pct, Be-6 pct) is isothermally transformed at high temperatures in the and y region after quenching from the fl field, the principal initial decomposition process is G one of growth of approximately spherical nodules composed of a number of lamellar colonies of the a and y phases. After the initial reaction has proceeded substantially or completely, depending on the transformation temperature, a second reaction occurs wherein the fine lamellar eutectoid is replaced by a coarser lamellar aggregate composed of the same oand yphases.' This reaction is not simply a spheroidization of the initial fine eutectoid but the nucleation and growth of a coarser, structurally different, and more stable distribution of the @and yphases. Fig. 1 illustrates the replacement of the initial fine lamellar structure by a coarse lamellar aggregate. The a phase is the dark mottled constituent; the light constituent the y phase. The phase diagram for the copper-rich end of the Cu-Be system2 is shown in Fig. 2. The a phase has the face-centered cubic structure characteristic of copper-rich solid solutions. The B phase is a disordered body-centered cubic structure, while the y phase is body-centered cubic, ordered (CsC1, B2 type). A. viswanathanS investigating Debye patterns of Cu-6 pct Be discovered that a transitory phase appeared on very rapid quenching from the /3 region which was absent when the quenching velocity was moderate. The phase could be assigned a body-centtred cubic structure with a lattice parameter of 2.876. Tempering at 100°C for 2 hr after quenching resulted in complete disappearance of the phase. The work of Fillnow and Mack' is the only previously published study of the isothermal transformation of eutectoid beryllium bronze. Their study elucidated the nature of decomposition at various subcritical temperatures in an exploratory fashion. The purpose of the research reported in this paper was principally to obtain quantitative information on the isothermal decomposition of the fl phase and to clarify the relationships existing between the fine lamellar eutectoid and the coarse lamellar aggregate. EXPERIMENTAL PROCEDURE The material used in this investigation was an almost eutectoid Cu-Be alloy bar furnished by D.J. Mack. The alloy had been melted under a protective carbon cover and centrigugally cast into a graphite mold preheated to 490 "C. Segregation was minimized by violent agitation during melting and pouring. The analysis of the casting was 93.85 pct Cu, 5.60 pet Be with traces of Si, Mg, Mn, Co, and Al. To determine the minimum soaking time necessary to insure specimen homogeneity, a number of specimens were held in the P region at 788OC for times fron 1 min to 12 hr and isothermally transformed at 550°C. Specimens betatized less than 12 min exhibited partial transformation at times shorter

Jan 1, 1961

By N. F. Dyson, T. R. Scott, M. R. Thornber, W. E. Ewers, M. Bussell

Leach liquors derived from the processing of nickel ores are generally highly contaminated and contain appreciable free acid. Methods are described for obtaining a commercial grade of concentrate from such solutions using pyrrhotite as the seed material to abstract nick- el, cobalt, etc. from solution. At temperatures in excess of 160° C., recoveries of 99% can be obtained from contaminated solutions where the free acidity is as high as 0.5 M in sulphuric acid. At lower temperatures down to 80° C., high recoveries can also be obtained either by adding H2S to the system with appropriate adjustment of the free acidity or by using "activated" pyrrhotite or artificial FeS in the system without prior addition of H2S. The methods are applicable to liquors derived from either oxide or sulphide ores, and the products are suitable for smelting or other known processes used to obtain pure metals. The mechanism of the reaction appears to vary with the operating temperature, and the results ye therefore discussed in the light of electron probe and optical microscopic studies.

Jan 1, 1973

By J. L. Taylor, Pol Duwez

THE present knowledge of the Ti-Al system is limited to the portion of the diagram extending from pure aluminum to the intermetallic compound TiAl3' A preliminary investigation of the titanium-rich Ti-A1 alloys revealed that the solubility of aluminum in titanium is quite extensive and that the transformation temperature of titanium is raised by alloying with aluminum. From an X-ray diffraction study of alloys containing up to 75 atomic pct Al (TiAl3), the phase boundaries at 750°C were located as follows: the a titanium solid solution extends from 0 to about 36 atomic pct Al, a two-phase region exists from 36 to 46 atomic pct Al, and an intermediate phase of varying concentration extends from 46 to 62 atomic pct Al. The purpose of the present paper is to describe the crystal structure of this new phase. The alloys were prepared by melting in a helium arc furnace on a water-cooled copper plate, using a furnace essentially the same as that described in ref. 2. The titanium metal was of the iodide type furnished by the New Jersey Zinc Co., and a piece of pure aluminum (99.99 pct) was obtained through the courtesy of the Aluminum Co. of America. After melting, the samples, weighing approximately 5 g, were sealed in evacuated fused silica tubes and homogenized for 4 hr at 1000°C. The specimens were then held for 10 days at 750°C and rapidly cooled to room temperature. Filings were then taken from each sample, sealed in evacuated vials, annealed at 750°C for 4 hr, and rapidly cooled to room temperature by quenching the vials in water. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using K copper radiation filtered through a nickel foil. Structure Determination The X-ray diffraction patterns of the alloys containing 46, 50, 55. 60, and 62 atomic pct Al were identical, except for a slight shift in the positions of the reflections. The alloy containing 55 atomic pct Al was chosen far structure determination. The powder pattern contained 37 reflections and the a, doublets were well resolved in the back-reflection range. The relatively small number of reflections and the sharpness of the pattern were considered as an indication of a simple atomic arrangement in a relatively small unit cell of high symmetry, and an attempt was therefore made to solve the structure without single crystal work. A satisfactory fit was found on a large scale Hull-Davey tetragonal chart for an axial ratio of approximately 1.45. All the reflections were readily indexed and the tentative unit cell dimensions were computed to be a - 2.81 kX, c - 4.07 kX, and c/a = 1.448. The indices (hkl) and the values of d and sin2 A are given in Table I. The agreement between observed and computed sin2 is quite satisfactory. Once the unit cell was known, the details of the structure were readily found. First, it is obvious that the number of atoms per unit cell cannot exceed two, since more than two atoms would lead to a density greater than that of pure titanium. The next logical step is to assume that the two atoms occupy the corner and center of the cell. If this assumption is correct, the structure may be described as follows: space group D1, - P 4/mmm; one titanium atom in a: 000; one aluminum atom in d: 1/2 1/2 1/2: and no extinctions. Assuming this structure to be the correct one. intensities were computed by means of the usual equation: sin2 0 cos 0 where F is the structure factor; 8, the Bragg angle. and p, the multiplicity factor. The calculated values of intensities are compared in Table I with the visually estimated intensities. The agreement is quite satisfactory and the structure is therefore confirmed. The crystal structure of TiAl just described is the same as that of AuCu ordered. The AuCu ordered

Jan 1, 1953

By Michael Hoch, Michel Desjardins

The isothermal section of the Mo-Ti-Zr-0 system at 1500°C was investigated using X- ray diffraction and mefallographic techniques. Up to 66.7 at. pct 0, the system contains ten four -phase regions. Isopleths at 10, 30, 45, 55, and 60 at. pct 0 were constructed. THE purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of molybdenum, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct o. PREVIOUS INVESTIGATIONS The Ti-Zr-0 system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by Hansen' and Levin, McMurdie, and Hall.3 Farrar, Stone, and Margolin studied the titanium-rich corner of the Ti-Mo-0 ternary. MATERIALS The titanium powder, 99.6 pct pure, the zirconium dioxide, and the molybdenum powder were supplied by the Fairmont Chemical Co. The zirconium powder,

Jan 1, 1962

By H. M. Day

THE constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were con-firmed and supplemented through X-ray analyses by Preston and Stenbeck.3 According to Murphy, at 276° C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower tempera-tures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region.

Jan 1, 1938

(Members are urged to send in for, this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period Aug. 10 to Sept. 10, 1915: Everett L. Booth, New York, N. Y. Raymond B. Ladoo, Cambridge, Mass. T. E. Sturtevant, Dover, N. J. Henry A. Tobelman, Ajo, Ariz. C. A: Filteau, New York, N. Y. R. B.Tinsley, B. Tinsley; Venezuela. Guy C. Riddell, Helena; Mont. ; E. H. Hamilton, Norfolk, Va. Joseph Leiner, New. York; N. Y. M. Yoshimura, Tokyo, Japan. Alfred W. G. Wilson, Ottawa, Canada. Van H. Manning has been appointed Director of the U.. S., Bureau of Mines, to succeed the, late, Dr. Joseph A. Holmes. Mr. Manning was Assistant Director of the Bureau. 0. M. Lewyn, formerly Mine. Superintendent for the Braden Copper Co., has accepted the position of Assistant Mine Manager with the Union Minière de Haut Katanga of South Africa.

Jan 10, 1915

NOMINATIONS FOR OFFICERS. In accordance with the Constitution, Article VII., the following nominations have been prepared by the Nominating Committee, submitted to the Board of Directors at its October meeting, and are hereby published for the information of the members. For Director and President: Benjamin B. Thayer, District 0 For Directors and Vice-Presidents: Herbert C. Hoover, District 6 W. L. Saunders, District 0 For Directors : Reginald W. Brock, District 11 Charles W. Merrill, District 6 Albert R. Ledoux, District 0 Henry L. Smyth, District 1 D. C. Jackling, District 7 The Constitution further provides that " Any complete or partial ticket of nominees signed by any twenty-five Members or Associates of the Institute and transmitted to the Secretary by December 15 shall also be printed and circulated with the official ticket and over the names and with the recommendations of the nominators, together with an expression of opinion of the Board thereon if deemed expedient.

Jan 11, 1913

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By Henry G. Granger, Edward B. Treville

The Republic of Colombia is the northernmost country of South America. Its northern coast line exteilds from the frontier of Costa Rica to that of Venezuela, on the Caribbean Sea. On the west it fronts on the Pacific Ocean, along the Panama Isthmus, and down to Ecuador. It is bounded on the south by Ecuador, Peru and Brazil, which latter country with Venezuela form its boundaries on the east. Its area exceeds 500,000 square miles. It is deemed unnecessary to give here a map of the country. Fig. 1, a map of the department of Antioquia, studied in connection with a good modern general map of Colombia, will explain itself. Fig. 1 contains also some of the region of the Cauca valley, described in this paper. Access.—The interior of Colombia is reached through the ports of Sabanilla and Cartagena on the Caribbean Sea, each of which places is connected with the Magdalena river by a short narrow-gauge railroad, running respectively to Barranquilla and Calamar. From these points lines of river-steamers serve the ports of the upper Magdalena, which they reach in journeys of a week to ten days. After leaving the steamer, a short railroad journey, followed by a long and tedious mule-ride, reaches the cities of Bogota and Medellin. Quibdo, at the head of the navigation of the Atrato, and its most important town, is connected by steamer-service with Cartagena, by canoe-routes with the various districts of the Choco, and by mule-road, at present well-nigh impassable, with the heart of Antioquia. On the western coast the port of Tumaco is a starting-point for canoe- and mule-travel to the southern part of the department of Cauca, while Buenaventura is the port of the central section of the valley of the Cauca,

Jan 1, 1899

By W. M. Courtis

THIS district commences near Pigeon River, the northeastern boundary between Minnesota and Province of Ontario, and extends entirely around the north shore of Lake Superior, terminating for the present at the Bruce Mines on Lake Huron. The discoveries of mineral-bearing veins have been confined for the most part to the lake shore, or to the country opened up by the Dawson Red River road. As yet the country back from the lake has been but little explored, on account of its roughness, being intersected by steep, rocky trap bluffs, 1000 or more feet high, and alternating white cedar and tamarack swamps. The forests are exceedingly difficult for prospectors. In many places Titanic piles of rocks, protected by chevaux-de frise of dead cedars, with their hooked, tough, sharp branches, and- a covering of spongy moss, sometimes several feet thick, successively guard against the discovery of hidden treasure. The Hudson's Bay Company for nearly a century have maintained trading-posts at Fort William and other points, which probably opened the way to the first discoveries that were made at Prince's Bay, near the western limit of the district. At this point a large vein was worked by Colonel Prince, the owner, as early as 1846. The richest part of the vein seems to have been on Spar Island, but work was stopped on account of excess of water. Sir William Logan states that a mass of ore weighing several hundred pounds and carrying 3 per cent. of silver was taken out. On the mainland small quantities of native and sulphide of silver were found, together with iron and copper pyrites, zinc blende, and galena, in a large spar vein. On the main shore a drift 165 feet long and 90 feet in depth

Jan 1, 1877

By W. A. Selvig

BY plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Com-mittee on Coal Classification. This scheme was sponsored by Sub-committee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic.. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as follows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group, 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. , The lignitic class of coal was divided into two groups both below 8,000.B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934

By W. M. Courtis

This district commences near Pigeon River, the northeastern boundary between Minnesota and Province of Ontario, and extends entirely around the north shore of Lake Superior, terminating for the present at the Bruce Mines on Lake Huron. The discoveries of mineral-bearing veins have been confined for the most part to the lake shore, or to the country opened up by the Dawson Red River road. As yet the country back from the lake has been but little explored, on account of its roughness, being intersected by steep, rocky trap bluffs, 1000 or more feet high, and alternating white cedar and tamarack swamps. The forests are exceedingly difficult for prospectors. In many places Titanic piles of rocks, protected by chevaux-de-frise of dead cedars, with their hooked, tough, sharp branches, and a covering of spongy moss, sometimes several feet thick, successively guard against the discovery of hidden treasure. The Hudson's Bay Company for nearly a century have maintained trading-posts at Fort William and other points, which probably opened the way to the first discoveries that were made at Prince's Bay, near the western limit of the district. At this point a large vein was worked by Colonel Prince, the owner, as early as 1846. The richest part of the vein seems to have been on Spar Island, but work was stopped on account of excess of water. Sir William Logan states that a mass of ore weighing several hundred pounds and carrying 3 per cent. of silver was taken out. On the mainland small quantities of native and sulphide of silver were found, together with iron and copper pyrites, zinc blende, and galena, in a large spar vein. On the main shore a drift 165 feet long and 90 feet in depth

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By W. H. Herrnstein, F. H. Beck, M. G. Fontana

Sulfur solubility in a iron was measured in the 750 to 890°C temperature range and was found to be insensitive to ferrite purity within a limited composition range. The permeability of sulfur in ferrite was determined from the internal sulfidation of Fe-Mn alloys. From the solubility and permeability results, the diffusivity of sulfur in ferrite could be calculated. These results are summarized as follows: Dissolved sulfur decreased the lattice parameter of ferrite. The effect of dissolved sulfur on the tensile properties of ferrite at low temperatures was also determined. SINCE sulfur is an important residual impurity in commercial irons and steels, effects associated with the presence of sulfur as a solute in iron are of considerable practical interest. Unfortunately, certain basic information relative to the Fe-S system appears to be lacking in the literature, e.g., the effect of dissolved sulfur on the lattice parameter and mechanical properties of ferrite. In addition, discrepancies exist in previously reported results for the solubility of sulfur in ferrite. These discrepancies raise questions regarding the sensitivity of sulfur solubility to the purity and microstructure of iron. This study was undertaken primarily in an effort to obtain reliable data on the solubility of sulfur in ferrite. Additional objectives included determination of the permeability and diffusivity of sulfur in ferrite by the internal sulfidation method and determination of the effect of dissolved sulfur on the lattice parameter and tensile properties of ferrite. EXPERIMENTAL METHOD Three grades of iron, encompassing a range of impurity levels, were employed in the study. The grades were designated VME (vacuum-melted electrolytic), SPZR (single-pass zone-refined), and MPZR (multipass zone-refined). The composition of each grade is given in Table I. Poly crystalline and single-crystal strip specimens were employed in the solubility experiments. Uniform grain size strip (ASTM 3 to 5) of 0.005 to 0.020 in. thickness was obtained by alternate cold reductions of 60 thickness 60 to 80 pct and recrystallization at 650°C for i hr in pure, dry argon. Single-crystal specimens were produced in 0.010-in.-thick SPZR iron strip by the strain-gradient anneal technique. Recrystallized strip 0.25 in. wide was strained until a Luders band or bands had propagated over the length of the strip; the strip was then annealed by drawing it through a 150°C per in. gradient (890°C peak temperature) at 1 in. per hr in an atmosphere of pure, dry argon. Laue photographs of the crystals produced exhibited no discernible asterism. Specimens were equilibrated with H-H, atmospheres at temperatures between 750" and 890" by one of two methods, each of which makes use of the reaction: The encapsulation sulfurization method was employed in the majority of the solubility experiments. A strip

Jan 1, 1969

By N. S. Stoloff, M. Gensamer

Pyramidal (1122) slip was observed in cadmium single crystals deformed in compression and bending at room temperature and —196°C. Crystals tested in tension twinned with no evidence of pyramidal slip. A critical resolved shear stress law for the propagation of twin nuclei appears probable. Twinning and low-stress kinking are believed to inhibit the appearance of pyramidal slip under ordinary experimental conditions. SEVERAL reports of nonbasal slip in cadmium have appeared in the literature recently, two of the reports having appeared after work on this project was in progress. Brown1 reported cross slip on electron micrographs, but did not identify the cross-slip plane. Wernick and Thomas2 observed nonbasal slip traces parallel to [1123] on a crystal bent with a pair of tweezers, but this too was an isolated observation, with no confirmation of the glide plane. The critical stress for pyramidal glide, and the temperature and strain rate dependence of glide on this system were not discussed. price3 has reported some observations of nonbasal slip in thin films of cadmium with the aid of transmission electron microscopy, but a full publication of these observations was not available at this writing. Pyramidal (1122) <1123> slip also has been observed on zinc single crystals4, 5 and (1122) <1010> slip on magnesium single crystals,6 all oriented with the basal plane nearly parallel to the specimen axis. Since the choice of slip system in the hexa- gonal metals is generally believed to depend on the axial ratio, with basal slip predominating for high-axial ratios, the occurrence of pyramidal slip in zinc and cadmium is unexpected. The objectives of the present investigation were to confirm the existence of nonbasal slip in cadmium, to identify the slip system, and to obtain an estimate of the critical resolved shear stress, assuming that the resolved shear stress law is applicable. EXPERIMENTAL PROCEDURE Two purities of cadmium, 99.95 pet and 99.99+ pet, were employed. As received bars were cold swaged to 3/16 in. rounds. Bicrystals and tricrystals were prepared by passing the polycrystalline rods through a gradient without seeds. It was desired to obtain a large yield of single crystals oriented xo* < 5 deg, in order to be able to suppress basal slip during deformation by keeping the resolved shear stress on the basal plane to a minimum. Cylindrical single crystals of cadmium were prepared by a seeding technique developed by Weiner,7 to obtain a predetermined orientation. The single-crystal rods were sectioned to specimen size by an acid-cutting technique originally developed for zinc crystals.&apos; An aqueous solution of nitric acid was the cutting agent. The acid was picked up by a plexiglass disc spinning at an optimum cutting speed through the acid, which was contained in a sump-like arrangement. The section to be cut, the acid bath, and the spinning disc were enclosed in a plexiglass case. The rod to be sectioned was coated with a thick layer of collodion. At the points at which sectioning was to be effected, the collodion was removed over a length of about 1/8 in. by dissolving it in acetone. To prepare a surface suitable for microscopic exam-

Jan 1, 1962

By Enid C. Plante

INTRODUCTION To extend our knowledge of the flotation behavior of sulphide minerals, the response of the following minerals to ethyl xanthate as collector was studied by captive bubble and cylinder flotation tests: antimonite (Sb2S3), arsenopyrite (FeAsS), covellite (CuS), marcasite (FeS2), orpiment (As2S3), pyrrhotite (FeS) and tetrahedrite (4CU2S, Sb2S3). Lollingite (FeAs2) was also examined to determine if its behavior could be correlated with that of pyrite or marcasite (FeS2). EXPERIMENTAL METHOD Mineral for Flotation and Contact Tests Mineral was prepared in the manner already described&apos; and its behavior both freshly ground and "oxidized" was studied. Tests in which the mineral was allowed to oxidize for various periods showed that a uniform response to xanthate was reached in two days or less. Oxidation Products The soluble oxidation products from most of the above minerals were measured and their effect on the flotation of the mineral studied. The mineral samples were wet ground to minus-52 mesh and deslimed, and 20 g of this material placed in 200 ml of distilled water of a measured pH value, and C02 free air bubbled through each suspension at a constant rate (about 1 bubble/sec) for 5 days. It has been shown1 that the size of the mineral is unimportant in the rate of formation of oxidation products and that probably the supply of oxygen to the mineral is the rate-determining step. At the end of 5 days the pH value of the supernatant liquid was measured again, the mineral filtered off and the soluble products determined. Methods for estimation of sulphur acids, ferrous and ferric iron and copper have already been described.1 No satisfactory method was found for antimony. Arsenic was estimated as the arsenate.2 FLOTATION OF "UNOXIDIZED" MINERALS WITH ETHYL XANTHATE AS COLLECTOR Fig I to 3, 4, 6, show the effect of alkali and cyanide as depressants for the minerals with 25 mg potassium ethyl xanthate per liter as collector at 35°C. Wark and Cox3 have shown that with ethyl xanthate as collector, galena, pyrite and chalcopyrite show a greater tolerance to cyanide and hydroxyl ions at room temperature than at 35°C. Covellite (Fig I), marcasite (Fig 2) and pyrrhotite (Fig 3) behave similarly. The independence of the curves for pyrrhotite at 35°C with respect to cyanide

Jan 1, 1947

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole&apos;&apos;) and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-&apos;) is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-&apos; using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- &apos; torr, Maiya and lakel measured y as 39 kcal mole-&apos; using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-&apos;: there is evidence also for a low temperature value of about 20 kcal mole-&apos;. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.&apos;-&apos;&apos; Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A&apos;, C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2&apos;3 M = mass of an evaporating molecule

Jan 1, 1970