Search Documents

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By William Glenn

In their account of chromium, Roscoe and Schorlemmer (Treatise on Chemistry, London, 1879) state that "In 1762 Lehmann, in a letter to Buffon, de nova minerœ plumbi specie crystalline rubra, described a new mineral from Siberia, now termed crocoisite." In 1786 Lehmann analyzed it (Nicholson's Jour., Dee., 1798) and found that it contained chiefly lead, and that the " mineralizers " were arsenic and sulphur. It was next examined in 1189 by Macquart and Vauquelin, who stated that it contained an intimate mixture of iron, alumina, and lead peroxide. The account of their work was published over the name of Macquart. Vauquelin (Louis-Nicolas) was a Norman peasant, who had studied in the village school, and at the age of fourteen was a laboratory-boy in a pharmacy at Rouen. Later, he found his way to Paris, and in 1789 was assistant to Fourcroy, a pharmacist and a teacher of note. It was here that he met Macquart, with whom he did the work on Siberian red lead, and at this time his friend Cheradame taught him his Latin.

Jan 1, 1896

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks' and to the precipitation of second phase particles,2'3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these '(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

Endurance Properties of Non-ferrous Metals Discussion of the paper of D. J. McADAM, JR., presented at the Syracuse Meeting of the Institute of Metals Division and issued, as Paper No. 1506-E, with Mining AND METALLURGY, October, 1925. H. F. MOORE,* Urbana, Ill. (written discussion).-This paper says that the results of tests of some non-ferrous metals made at the University of Illinois and in the testing laboratories at McCook Field are abnormal when they do not agree with results obtained by the author. The writer can see no inherent reason why results of the type uniformly reported in this paper are any more normal. The knee of the stress-cycle, or S-N, diagram comes at different lengths of life for different metals. For steel, the knee occurs after from 1,000,000 to about 4,000,000 cycles, and for some non-ferrous metals not before 20,000,000 of 30,000,000 cycles. The writer can see nothing inherently abnormal in finding certain nonferrous metals for which the knee of the stress-cycle curve occurs at 1,000,000,000 cycles or higher. The writer has had experience with both the cantilever and the rotating-beam testing machine, and thinks that the chance of whipping action in the cantilever machine is a more serious handicap than the action the author has pictured. Furthermore, the writer questions whether the author has shown the existence of a clearly marked and definite endurance limit for all the non-ferrous metals he has tested including the following: Nickel (CT and A-16, Fig. 1), monel (CS-5.5 and BK, Fig. 2), bronze (F and CK, Fig. 4), aluminum bronze ( BJb-1, Fig. 6).

Jan 12, 1925

A national budget system, which engineers have long regarded as essential to the proper conduct of our fiscal affairs is at last being seriously considered by. Congress and seems likely to be adopted in some form. Several, bills and joint resolutions have already- been introduced but the measure that seems how to attract the 'most attention is H. R. 1201 introduced by. Representative Good, Chairman of the House Committee on Appropriations. This ,bill provides for the creation of a Bureau of the Budget in the office of the President, to which full information shall be furnished by all Departments and other Governmental agencies concerning powers, duties, financial transactions, business method's, etc. A change, is made in the fiscal regulations in that the Departments shall hereafter submit their fiscal estimates to the President instead of to the Secretary of the Treasury, while the latter official shall submit estimates of the public revenues and the condition of the Treasury. Two budgets are, provided for:, The first, or regular, budget shall contain a balanced statement of the resources and liabilities of the Government and the revenues and expenditures, actual or estimated as the case may be, for the preceding, current, and ensuing fiscal years. The President is further, authorized to submit his recommendations as' to how the heeds of the Government should be met, and such further data regarding the financial affairs of the, Government as he deems proper. The second or alternative budget shall make known the essential facts regarding the condition of the Treasury and what, in the opinion of the President. are the revenue, and expenditure needs for the ensuing fiscal year, to be prepared in such form as the President shall deem most appropriate. The bill' abolishes-the offices. of Comptroller of the Treasury and all -the Auditors for the several Departments, and substitutes therefore an Accounting Department, an establishment independent of the Executive Departments, under the direction of newly created officer to be known as the "Comptroller General of the United States" whose powers shall comprise all those now conferred on the Comptroller of the Treasury and the several Auditors and, in addition thereto, the investigation at the seat of Government or elsewhere of all matters relating to the receipt or disbursement of public funds, concerning which report shall be made to Congress at the beginning of each regular session, containing recommendations concerning the legislation deemed necessary to the accurate rendition and settlement of accounts.

Jan 8, 1919

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York, L. W. FRANCIS, Chairman, WILLARD S. MORSE, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN, Treasurer. LOUIS D. HUNTOON. WILLIAM A. POMEROY. Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. ROBERT H. RICHARDS, ALBERT SAUVEUR. Columbia FRANK A. ROSS Chairman. RUSH J: WHITE, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. FREDERIC KEFFER FRANCIS A. THOMSON,

Jan 2, 1915

By Stephen Burke

THE oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combus-tion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the condi-tions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 21120 + 702 --> 2FeSO4 + 2H2S04 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to dis-close any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1937

By Tegner C. Johnson

Just a few years ago, my company was referred to as the Marion Steam Shovel Company. Though we still make shovels, both two and eight-crawler types, the eight-crawler stripping shovel appears to have been replaced by the walking dragline for overburden removal and in some cases for the mineral as well. The walking dragline appeared in the coal fields in the early 1930's. It is popular because it can cope with overburden depths in excess of 100 ft and with blasted sedimentary rock, all at an O & O (ownership and operational) cost of ±10[c] per bank cu yd (bcy).

Jan 10, 1974

[Holds monthly meetings, except June, July and August, J JOHN A. CHURCH, JR., Chairman JOSEPH E. POGUE, Vice-chairman SIDNEY ROLLE, Vice-chairman EDWARD C, MEAGHER, Secretary, Texas Gulf Sulphur Co,, 41 E, 42nd St., New York M, H, MERRISS, Treasurer, 42 Broadway, New York ARTHUR NOTMAN T. T, READ Boston Meets first Monday of each winter month. EDWARD C. GEITHER, Chairman WILLIAM S. BLACK, Vice- chairman DONALD H, MCLAUGHLIN, Secretary, treasurer, Rotch Bldg,, Harvard Univ,, Cambridge, Mass. J, L. GILLISON A. G, WAITE]

Jan 1, 1928

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1' to 10' of arc, but values of UP to 20' have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By A. W. Schlechten, R. F. Doelling

Parkes' process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,' raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes' crusts by one of the authors' gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes' process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes' crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper' on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned' supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

COMMITTEE OF ARRANGEMENTS. General Committee.-J. F. Lewis, Quinnimont, W. Va. Committee of Reception at Staunton.-Major Jed. Hotchkiss, Chairman ; W. A. Burke, M. E. Miller, R. N. Catlett, W. J. Nelson, J. T. Effinger, D. A. Kayser. Local Committee of Arrangements.-G. T. Wickes, Low Moor, Chairman; G. W. Bramwell, Stone Cliff, Secretary; J. E. Johnson, Longdale; H. Firm¬stone, Longdale; S. F. Morris, Quinnimont; O. A. Randall, Ferrol; William N. Page, Ansted; F. Lyman, Low Moor; S. M. Buck, Coalburgh; E. S. Hutchinson, Cannelton ; M. F. Maury, Saltpetre Cave. THE opening session of the Institute was held at Staunton, on Monday evening, May 30th, in the Opera House. Major Jed. Hotchkiss, Chairman of the Committee of Reception, called the meeting to order and introduced Mayor Balthis, who spoke a few words of welcome to the members present, and then introduced the Hon. A. H. H. Stuart. Mr. Stuart in addressing a formal welcome to the Institute to the " little city of the mountains," spoke of the value of the services of the mining engineer in developing the mineral wealth of Virginia and in solving the problems of her geological history. Mr. Metcalf, President of the Institute, replied on behalf of the Institute to the cordial welcome of the mayor and Mr. Stuart, and then read an inaugural address on Force. At the conclusion of the President's address the following papers were read The Electrolytic Determination of Copper and the Formation and Composition of so-called Allotropic Copper, by J. B. Mackintosh, Hoboken, N. J. Read by Professor Egleston. The New Unpublished Map of Chester County, Pa., by Professor Persifor Frazer, Philadelphia. The second session was held at the Opera House on Tuesday morning. The papers read at this session were: Investigations on the Ore Knob Copper Process, by Professor Thomas Egleston, School of Mines, New York city. A Volumetric Estimation of Manganese in Pig Iron and Steel, by F. H. Williams, Vulcan Steel Works, St. Louis, Mo. Read by the Secretary.

Jan 1, 1882

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York L. W. FRANCIS, Chairman. WILLARD S. MORSE, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN; Treasurer. LOUIS D. HUNTOON. WILLIAM A. POMEROY Boston HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. ROBERT H. RICHARDS, ALBERT SAUVEUR. Columbia FRANK A. ROSS, Chairman. RUSH J. WHITE, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. FREDERIC KEFFER, FRANCIS A. THOMSON.

Jan 1, 1915

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

Executive SIDNEY .J. JENNINGS, Chairman GEORGE D. BAR HON .I. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, chairman LEWIS W. FRANCIS .1. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR. L. WALKER Finance GEORGE D. BARRON. Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY1 Chairman ALEX C. HUMIPHREYS3 GEORGE C. STONE .J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 10, 1918

New Products Equipment

Jan 6, 1953

By E. H. Dix

During an investigation of high-strength manganese bronze by til Engineering Division of the Air Service, at McCook Field, Dayton, Ohio, particles of a "blue constituent" were noted in the microstructure of most of the bronzes examined. The constitution of the simple copper-zinc base alloy is still a matter of dispute in spite of the fact that the copper-zinc series is one of the oldest industrially important groups of alloys, and has received thc carly co~l+itlcl-ntio11 of scirntific rcsc:trch. Thc diagram, according to the rnost rcrent \vork.' IS shown in Fig. 1. The disputed questions involve the tcrmi~r:~tiorl of the beta field and the lint at 470' C. The parliest expc~imc>ntcr, Rol)erts--~1~11stcri, detectrd an arrest in some of his cooling curves :it approximately this temperature and ascribed them to the formation of a cutectic; it has since been proved that there arc no eutectics in this series. Shepherd? was unable to detect any thermal arrests at this temperature, his. diagram was essentially as shown in Fig. 1, except that the line at 470" ('. was omitted and the beta phase carried down to normal temperature. 1,:ttcr. carpenter and Edwards, by a very painstaking research, definitely established the authenticity of the line but attributed it to the breakdown of the BETA constituent into a cutectoid of alpha and gamma. microscopic evidence of the formation of the cutectoid is doubtful and it seems more likely to he due to an allo-tropic change in the beta constituent as shown by Fig. 1. At least for practical purpose?, it is more convenient to think of the structure of a 60-40 brass as a mixture of alpha and beta prime crystals rather thin alpha plus an unresoluble eutectoid of "apparent beta" as it has often been called. * Chief, Metals branch, Engineering Division, Air Service. 1 0. F. Hudson: Jnl. Inst. of hlvtals (1913) 12, 2 E. S. Shepherd: Jnl. Phys Chrm. (10141 8, 421. H. C. H. Carpenter and O. A. Edwards: Jnl, Inst. of Metals (1911) 5, 127.

Jan 1, 1923

By E. H. Dix

During an investigation of high-strength manganese bronze by til Engineering Division of the Air Service, at McCook Field, Dayton, Ohio, particles of a "blue constituent" were noted in the microstructure of most of the bronzes examined. The constitution of the simple copper-zinc base alloy is still a matter of dispute in spite of the fact that the copper-zinc series is one of the oldest industrially important groups of alloys, and has received thc carly co~l+itlcl-ntio11 of scirntific rcsc:trch. Thc diagram, according to the rnost rcrent \vork.' IS shown in Fig. 1. The disputed questions involve the tcrmi~r:~tiorl of the beta field and the lint at 470' C. The parliest expc~imc>ntcr, Rol)erts--~1~11stcri, detectrd an arrest in some of his cooling curves :it approximately this temperature and ascribed them to the formation of a cutectic; it has since been proved that there arc no eutectics in this series. Shepherd? was unable to detect any thermal arrests at this temperature, his. diagram was essentially as shown in Fig. 1, except that the line at 470" ('. was omitted and the beta phase carried down to normal temperature. 1,:ttcr. carpenter and Edwards, by a very painstaking research, definitely established the authenticity of the line but attributed it to the breakdown of the BETA constituent into a cutectoid of alpha and gamma. microscopic evidence of the formation of the cutectoid is doubtful and it seems more likely to he due to an allo-tropic change in the beta constituent as shown by Fig. 1. At least for practical purpose?, it is more convenient to think of the structure of a 60-40 brass as a mixture of alpha and beta prime crystals rather thin alpha plus an unresoluble eutectoid of "apparent beta" as it has often been called. * Chief, Metals branch, Engineering Division, Air Service. 1 0. F. Hudson: Jnl. Inst. of hlvtals (1913) 12, 2 E. S. Shepherd: Jnl. Phys Chrm. (10141 8, 421. H. C. H. Carpenter and O. A. Edwards: Jnl, Inst. of Metals (1911) 5, 127.

Jan 1, 1923

By H. H. Taft

IT has long been known that the volcanic area south of Belmont, Nye county, Nevada, had mining possibilities. Some of the old-time prospectors knew that gold existed there. Its remoteness from any source of supplies, its long distances from water, the absence of game, and more, perhaps, the lack of grass for animals to subsist upon, has made this an unattractive region in which to search for mines. The decline of the Comstock mines, the exhaustion of sun-dry large and rich ore-bodies, the high cost of mining, marketing, and particularly the ruinously high freight-charges upon refractory ore that had to be shipped to distant smelters, have kept investors out of Nevada for the last few years; and mining people have hardly yet awakened to the importance of Tonopah, Goldfield and perhaps the newer and less developed districts. The discovery of Tonopah by J. L. Butler, who located the Mizpah Claim in May, 1900, and the fortunes soon realized there, attracted many people. As the boom declined, many went away, some scattering out into the surrounding country, and the population is now about 7,000. In the fall of 1902 a discovery of gold was made 23 miles south, in what is now known as the Sandstorm group, 4 miles NW. of Goldfield. In the winter of 1903-4 the Combination, January and Florence mines were discovered, and shipments of high-grade ore soon followed. In January, 1905, there were 10,000 people in Goldfield. In June, 1904, rich gold-ore was found 85 miles SE., at the foot of the south end of the Kawich mountains, but this discovery was kept quiet until a re-location could be made. On August 10, 1904, the Bullfrog claims, and a month later the Ladd mountain and neighboring claims, were located. The Shoshone group was located September 24. This district is

Nov 1, 1905

By M. H. Waxman, M. Gondouin, H. J. Hill

Streaming-potential experiments were conducted within the Muddy- and Dakota-sandstone interval of a Denver basin well. Analysis of the data shows that, for this case, streaming potentials opposite sands were higher than those opposite shales when the mud was fresh. Streaming potentials opposite shales, however, were of sufficient magniiIlde to be important in SP interpretation. They were linearly dependent upon pressure differential, and they increased with mud filtrate resistivity. The magnitude of streaming potentials opposite sands was influenced by the characteristics of the original mud cake formed at the time of drilling. Use of mud samples taken at the time of logging may not always be satisfactory for determining streaming-potential corrections. Both the streaming and electrochemical potentials were found to be affected by the previous history of the borehole system. Following a change in mud characteristics, several days were required for SP stabilization. This was, in part, due to the mud cake acting as an imperfect shale membrane. INTRODUCTION Laboratory investigations by Wyllie,1 Salisch,2 Moore," Sen Gupta and Bannerjee,0 and Hill and Anderson' have shown that streaming potentials developed across mud cakes deposited on permeable filter beds are of sufficient magnitude to be critically important in SP interpretation. Streaming potentials across shales have been reported by Schenck,' Gondouin and Scala; and Hill and Anderson." The magnitude of the shale streaming potentials obtained by Schenck and by Gondouin et a1 led these authors to conclude that in many cases the shale streaming potential would approximately equal the mud-cake streaming potential. Hill and Anderson, however, obtained somewhat lower magnitudes of shale streaming potential. The field experiment described in the present paper was a cooperative project carried out by the respective operations and research departments of Schlumberger Well Surveying Corp., Shell Development Co. and Shell Oil Co. The primary objective of the experiment was to determine in the borehole the streaming-potential behavior of both shales and mud cakes under conditions approaching, as nearly as possible, those normally encountered in logging practice. METHODS AND EQUIPMENT WELL A Muddy- and Dakota-sandstone vie11 in the Denver basin was chosen for the experiment. Both sandstones were water-bearing and, since reservoir pressures in these sandstones are abnormally low (gradient of approximately 0.25 psi/ft), it was expected that studies of streaming potential could be conducted from low-pressure differentials (approximately 200 psi) to about 27000 psi by bailing mud from the hole, filling up and then applying wellhead pressure. The selected well encountered the Muddy sand-