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By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,' the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

At Asarco's Mission mill. located near Sahuarita, Ariz., the 20 500-t/d (22,500-stpd) throughput of highly abrasive and corrosive copper ore can play havoc on equipment wear parts. To minimize frequent replacement work and extend life on key components, Asarco engineers have over the past five years utilized liners made of "Towniprene" in the secondary grinding and flotation area of the plant. Results to date have indicated that these liners last between three and five times longer than those made of metal or ordinary rubber.

Jan 8, 1978

By C. A. Meissner

THE following is a further discussion of the paper of James Gayley, " The Application of Dry-Air Blast to the Manufacture of Iron " (Trans., xxxv., 746), with special reference to his sup-plementary paper (Bi-Monthly Bulletin, No. 4, July, 1905, pp. 797 to 819), and. to the paper of J. E. Johnson, Jr., "Notes on the Physical Action of the Blast Furnace " (Bi-Monthly Bulletin, No. 5, September, 1905, pp. 1111 to 1146). Mr. Gayley's paper has been discussed also by E. Windsor Richards, R. W. Raymond, E. H. Saniter, W. J. Foster, H. M. Howe, V. Pendred, B. H. Thwaite, James Gayley and Alexander Pourcel (Trans., xxxv., pp. 1022 to 1042), Joseph W. Richards (Bi-Monthly Bulletin, No. 4, July, 1905, pp. 703 to 718); T. W. Robinson (Bi-Monthly Bulletin, No. 4, July, 1905, pp. 788 to 796) ; C. B. Dudley, R. W. Raymond, J. E. Johnson, Jr., W. F. Mattes, James Gayley, David Baker, John Birkinbine and F. E. Bachman (Bi-Monthly Bulletin, No. 5, September, 1905, pp. 1147 to 1152);.E. de Mille Campbell (Bi-Monthly Bulletin., No. 1, January, 1906, pp. 25 to 50) ; John Birkinbine (Bi-Monthly Bulletin, No. 1, January, 1906, pp. 137, 138). At the Washington meeting of the Institute, May, 1905, a very instructive and interesting paper was presented by Mr. J. E. Johnson, Jr., entitled " Notes on the Physical Action of the Blast Furnace,"' in which reference is made to Mr. Gayley's dry-blast process. A few of Mr. Johnson's conclusions, as summarized in the last pages of his paper, do not appear to me to be in complete accordance with the results obtained at the Isabella furnaces; and I therefore present the following notes which may throw further light on this subject: Mr. Gayley has called attention to the fact that the moisture in the air is an extremely variable and uncertain factor; and

May 1, 1906

By Walter S. White

The Michigan native-copper district has produced about 5,400,000 tons of copper since mining began in 1845. The copper occurs primarily as open-space fillings and replacements in amygdaloidal flow tops and conglomerate beds of the Portage Lake Lava Series, of middle Keweenawan age. Secondary minerals with which the copper is associated include microcline, chlorite, epidote, pumpellyite, prehnite, quartz, and calcite; zeolites, other than laumontite, are not abundant. A zonal pattern of the secondary minerals transects bedding and suggests regional metamorphism mainly to the grade of the prehnite-pumpellyite graywacke facies of Coombs. Most of the major copper deposits are near the upper limit of abundant quartz in this zonal pattern. The distribution of copper in both amygdaloid and conglomerate deposits is controlled partly by primary permeability of the rocks and partly by later tectonic fracturing that was concentrated in the mechanically weak flow tops and sedimentary beds. Ore shoots and deposits are therefore controlled partly by primary structural features, such as areas of thick and thin fragmental amygdaloid or the boundaries of conglomerate lenses, and partly by regional structure: a number of ore deposits are in synclinal downwarps. The copper-bearing solutions that formed the deposits were ascending. They may have come from a large concealed intrusive, or may have been driven out of the porous tops of lava flows when the rocks were compacted and metamorphosed at great depth in the central part of the Lake Superior syncline. The second hypothesis seems more consistent with the widespread distribution of the copper, its relation to mineral zoning that represents truly regional metamorphism, its native state, and the likelihood that copper deposition was later than most or all of Keweenawan volcanism.

Jan 1, 1968

By Hiram B. Woon

Uranium ore deposits in the Lisbon Valley area are in an arcuate belt, 15 miles long by one-half-mile wide, on the southwest flank of the Lisbon Valley anticline. They range in size from 500 to 1,500,000 tons and by mid-1965 had yielded 6,147,000 tons containing 48,530,000 pounds of U3O8. Ore bodies average 6 feet thick, are tabular, amoeba-shaped masses, concordant to the bedding, and are in the thickest, lowest sandstone unit of the Moss Back Member of the Chinle Formation of Triassic age. The host rock is predominantly a fluviatile, calcareous, fine-grained to conglomeratic sandstone. Uraninite, the principal ore mineral, fills the pores in the sandstone and partly replaces sand grains and fossil wood fragments. During Late Permian and Early Triassic time pre-Chinle Formations were arched to form the ancestral Permian anticline. Moss Back streams truncated Moenkopi and Cutler beds which capped the ancestral anticline and then covered it with fluviatile elastics, which were subsequently covered by thousands of feet of Triassic, Jurassic, and Cretaceous sediments. Uranium, probably derived from the Chinle Formation by diagenetic processes, was transported in connate ground waters, was moved by compaction or hydrostatic forces, and was deposited under reducing conditions. Uranium was emplaced around the crest of the ancestral anticline, prior to the Laramide orogeny. During the orogeny, the Tertiary-Lisbon valley anticline was super induced on the Permian anticline and, penecontemporaneous with uplift, was faulted parallel to its longitudinal axis. The Big Indian ore belt on the southwest flank footwall block was elevated to approximately its present position, and the northeast flank hanging wall block was elevated only slightly. An extension of the Big Indian ore belt around the northeast flank of the ancestral Permian anticline may exist in the Moss Back sandstone in the downthrown block northeast of the Lisbon Valley fault.

Jan 1, 1968

By T. A. Rickard

An educated man is distinguished neither by his clothes nor by his knowledge; he is replarkable not for the things he says, but for the way he says them. You cannot even stand with him under an archway in the rain without finding him out. He may talk only of the weather. His words and his phrases alike may be simple. -at distinguishes him is the arrange- ment of his words; however desultory his talk, it will be method- ical; he has habituated himself to foreseeing the part to be played by each word he uses and the place to be taken by each sentence he utters. On the other hand, the uneducated man, though shrewd and well-informed, will relate facts and events as they recur to him, generally in disorder; in his effort to recollect and in his attempt to rectify forgetfulness he will pause irregularly, filling the intervals with meaningless phrases, such as "and then ", "and: so ", or 'said he to me", "said I to him"; and even the contipuous parts of his story will be told confusedly-because he has not learned the proper use of words.* My own experience as an editor of technical manuscripts has taught me that the misuse of 'that' and 'which' is a fruitful cause of obscurity and confusion. The relative pronouns have distinct functions, and no writer can express himself clearly until he has learned to discriminate between these I functions. For example:

Jan 1, 1931

By Thomas T., Read

IT will be recalled that the first professor of metallurgy in the United States, appointed in 1855, never really gave any instruction in metallurgy and gradually turned into a professor of mineralogy. Metallurgy was included with. mining in the early curricula, two students who took the B.S. in mining engineering from the Polytechnic College of Pennsylvania in 1862 wrote their graduation theses on the metallurgy of copper and zinc, respectively. Even after Columbia School of Mines established, in 1868, a separate curriculum leading to the Ph.B. degree in metallurgy, very few students elected it,* preferring to take the mining degree, since they received in its curriculum nearly all the metallurgical instruction they would have in the metallurgical curriculum. For many years a large proportion of the men who attained prominence in metallurgical enterprises had taken mining rather than metallurgical degrees. METALLURGY Clifton Sorby's study of thin sections of rocks under the micro¬scope, beginning in 1850, and its subsequent development by Zirkel and others, had made microscopic petrography a recog¬nized department of geological research as early as 1873. . It was inevitable that the idea of studying polished metal surfaces-¬under the microscope by reflected instead of transmitted light would occur to investigators. Sorby himself did it in 1864, and Adolph Martens and Floris Osmond may -be especially named among the many European workers who, by the late eighties, had so developed the, necessary techniques that they were able to photograph polished metal surfaces at magnifications as high

Jan 1, 1941

THE John Fritz Medal Board of Award, at its regu¬lar annual meeting Oct. 19, awarded its gold medal to Herbert Clark Hoover. Thus ended a process of selection begun a few years ago. The award was tentatively made a year ago by the Board, which is composed of sixteen recent past-presidents of the four national societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers, having together a membership of nearly 60,000. The sixteen members of the Board are: American Society of Civil Engineers : C. E. Grunsky, Robert Ridgway, George S. Davison and John F. Stevens ; American Institute of Mining and Metallurgical Engineers: William Kelly, J. V. W. Reynders, Samuel A. Taylor and E. DeGolyer; American Society of Mechanical Engineers: Fred R. Low, D. S. Jacobus, Dexter S. Kimball and Charles M. Schwab; American Institute of Electrical Engineers: Farley Osgood, M. I. Pupin, C. C. Chesney and Bancroft Gherardi.

Jan 1, 1928

By ALEXANDER L Hay, Alexander L.

THE Sydney coal field, the largest and most valuable in Nova Scotia, is on the northeastern coast of the Island of Cape Breton, extending from Mira Bay on the south to Cape Dauphin on the north, a distance of 30 miles, and has a general dip northeast under the sea. The field embraces the mining villages of Morien, Birch- grove and Reserve and the towns of Dominion, Glace Bay, Waterford and Sydney Mines. The city of Sydney is about midway between the northern and southern extremities of the field and on the western fringe of the productive coal measures. Sydney harbor crosses the coal field, cutting off direct rail connection between Sydney Mines and the greater part of the field to the southeast.

Jan 1, 1928

By R. V. Norris

LAST October, Mr. R. V. Norris and Mr. Matthew C. Fleming were appointed to represent the Institute at the Second National Industrial Tax Conference, which was held in New York City on Oct. 22 and 23. After reading the report submitted by the Committee, Mr. Norris and Mr. Fleming addressed the following to the Tax Committee of the National Industrial Conference Board: The tentative report of the Tax Committee of the National Industrial Conference Board was received too late to make it possible to lay it before the Board of the Institute, and the undersigned themselves have not had sufficient time to digest its interesting contents and recommendations carefully. So that we desire to make it clear that the comments we make on the report are the expression of our personal opinion only. In the first place, we feel that the Committee which drew this tentative report is entitled to the commendation and thanks of the country for what has been manifestly a work of tremendous labor and for the able and conservative report which they have presented. With

Jan 1, 1921

By R. D. Rubright, Owen J. Hart

In the Bingham district over a span of more than 90 years, 43,947,104 tons of "non-porphyry" copper, lead, zinc, gold, and silver ore have been mined from a folded and faulted alternating series of Pennsylvanian and Permian limestones and sandstones and from some Tertiary intrusives. This ore came from six major mine areas located east, south, and west of the Bingham stock, site of Kennecott's porphyry copper deposit. The sediments were affected by varying degrees and types of metamorphism within 2000 feet or more of the Bingham stock. The intrusives consisting of the mineralized Bingham and the unmineralized Last Chance stocks and numerous dikes and sills of granite and monzonite were intruded into the asymmetrical northwest-trending and plunging Bingham syncline. Extrusives, although present, contain no ore. The bulk of the non-porphyry ore in the district was found above the Midas thrust. The primary ores are found in three major types of deposits: concordant bedding fissures, crosscutting fissures, and replacement deposits. These deposits consist of both copper and lead-zinc ore bodies that contain various amounts of gold and silver. These are in places roughly zoned both laterally and vertically and have been mined for up to 10,000 feet outward from the center of the Bingham stock and up to 5000 feet vertically below the surface. Secondary ore was of minor importance and was found in and under the oxidized zone at shallow depths. Genetically the Bingham stock, the ores, and related phenomena have had a common source.

Jan 1, 1968

By Edward C. Stephens, Robert R. Coats

High-grade copper ore was discovered in 1932 in the long-dormant Mountain City (Cope) mining district, Elko County, Nevada. From 1932 to 1947, the one producing mine in the district, the Mountain City Copper Mine, produced 1,109,878 short dry tons of ore averaging 9.745 per cent copper, 0.274 ounces of silver, and 0.0057 ounces of gold per ton. The Mountain City Copper Mine is developed in eugeosynclinal rocks of Ordovician age, the Valmy Formation, which is part of the upper plate of the Roberts Mountains thrust. On the Valmy were deposited unconformably first, a elastic formation of Devonian or Mississippian age, the Grossman Formation, succeeded unconformably by a ·sequence of three conformable formations, the Banner, the Nelson, and the Mountain City. The Banner Formation probably is early Late Mississippian in age; the ages of the Nelson and Mountain City are not known precisely but are believed to be of Late Mississippian and Carboniferous(?) age, respectively. A thick formation of elastic rocks, limestone, and volcanics, the Reservation Hill Formation, has been thrust over the Mountain City. The age of the Reservation Hill is unknown but is presumed to be Pennsylvanian(?) and Permian(?). Several plutons of Cretaceous quartz monzonite intrude the Paleozoic formations; they and the intruded formations have been laid bare by erosion, and several sequences of volcanic rocks of Miocene and Pliocene age, and perhaps in part older, have been successively deposited on irregular erosion surfaces. The primary mineralization of the Mountain City Copper Mine is believed to postdate the deposition of the Nelson Formation and to predate the intrusion of the quartz monzonite. The primary ore bodies are lenticular in shape and are composed largely of quartz, pyrite, and chalcopyrite. The ore lenses, in general, strike northwestward and dip northward. They occur in the Valmy Formation within a definite stratigraphic sequence composed largely of shales with associated minor quartzite lenses. The ore is epigenetic. The principal ore body, the "200," was completely leached to the 200 level. Abruptly beneath the barren gossan was supergene copper sulfide ore, much of which assayed 50 per cent copper. The secondary copper minerals are sooty and massive chalcocite, bornite, and covellite. The supergene enrichment of the ore may have required a large part of Tertiary time.

Jan 1, 1968

By Paul F. Kerr, Donald M. Hausen

Fine colloidal gold near Carlin, Nevada is disseminated in leached carbonate strata of the Roberts Mountains Formation in the Lynn "window" of the Roberts Mountains thrust fault. The ore body is generally stratiform and is more or less conformable to altered beds near the top of the formation, underlying Devonian limestones. Two sequences of mineralization are recognized: ( 1) an earlier base metal-barite assemblage related to early Cretaceous intrusives (121 ± 5 m.y.), and (2) a later low temperature Au-As-Hg-Sb assemblage of near surface emplacement. The earlier sequence consisting of sparse galena and sphalerite in barite with anomalous amounts of zinc, lead, nickel and copper, associated with dikes of dacitic composition, is of little economic importance. The later sequence of gold, realgar, cinnabar, and stibnite associated with extensive silicification and argillic alteration of limestone beds, has resulted in important deposits of gold. Argillic alteration of hydrothermally leached carbonate strata has provided the environment in which the most prominent gold deposition took place. Carbonate minerals in the limestone host rock have been replaced by microcrystalline quartz and chalcedony to form stratiform silica masses and recrystallized lenses of euhedral quartz. Zones of porous silicification are light gray to white, elliptical in shape, and more or less follow bedding. Silicification is bordered by argillic alteration and pyritization. Deposition of gold usually lies in a zonal pattern that encircles chimney areas of silicification.

Jan 1, 1968

By OTTO HERRES

TO operate the bituminous coal industry in the United States in 1929 cost $770,237,000, of which $30,739,000 was paid for purchased power and $34,947,000 for new machinery and equipment. Equipment aggregated 3,124,000 hp. A mining industry that spends $65,000,000 a year for power and machinery is likely to be fairly well mechanized, and when the machinery in use takes three million horsepower to drive it, the probabilities are that mechanization has been in progress in at least some of the mines for quite a few years. Mechanization in its broadest sense implies machine cutting, power drilling, mechanical loading, electric haulage, mechanical sizing and cleaning, and lesser applications of machinery to mining operations. But the introduction and development of mechanical loading has been the feature of coal mining recently and its extraordinary progress is causing great changes within the industry. First, let us look at the records. The quantity of coal loaded mechanically in bituminous mines was:

Jan 1, 1933

By Marvin P. Barnes, John G. Simos

The Park City District, Utah, is situated in the Wasatch Range at the intersection of the westward extension of the axis of the Uinta Range. Ore has been mined almost continuously from the first discovery in 1869 to the present day, with a total production of over 14 million tons. Sediments of Carboniferous to Triassic age have been folded into the northerly plunging Park City anticline and subsequently modified by thrust faulting, diorite and diorite porphyry intrusions, and strong east-west normal faulting during the Laramide orogeny. Younger andesitic volcanics partially cover the eastern edge of the district. The ore bodies occur as both lode and bedded replacement deposits over widely scattered localities. Near surface, high-grade silver "bonanza" ores were mined in early days from the Ontario and Daly Lodes, which occur along the east-west zone of faulting near the center of the district. Other lode or fissure deposits were found along the Mayflower and Hawkeye faults to the east and southeast. Large bedded replacement silver-lead-zinc ore bodies associated with east-west zones of fissuring, have been mined from favorable horizons in the Park City Formation in the Daly West and Judge mines. A series of long, narrow, high-grade, replacement ore bodies occur in the Silver King mine at a single horizon in the Park City Formation. Ore is currently being mined from strong bedded replacements in the Humbug Formation near the apex of the Park City anticline. Factors controlling ore deposition are: magmatic source, structural feeder systems, and favorable host rocks. Ore deposition along favorable beds is primarily a function of physical conditioning and secondarily of chemical composition.

Jan 1, 1968

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400&apos;F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y&apos; precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y&apos; precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10&apos; to 10&apos; cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975&apos;F for 4 hr.

Jan 1, 1970

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By Y. C. Liu, G. A. Alers

measurements of the anisotropy in Young&apos;s modulus produced in copper by rolling 95 pct reduction in thickness below room temperature have been carried out in order to study the dependence of the texture on rolling temperature. The results clearly show the transition from a copper-type texture to a brass-type texture as the temperature of rolling is lowered. The intermediate textures observed can be described very well as a simple mixture of the two terminal textures. These results cormbined with other texture measurements make possible afresh review of the experimental facts velating to rolling textures in fee metals and, as a consequence, a critical examination of the current theories is presented. PREVIOUS experiments have shown that the transition from the copper- to the brass-type rolling texture is clearly displayed and can be quantitatively analyzed by measurements of the anisotropy of Young&apos;s modulus.&apos; Application of this method to the Cu-Zn alloy system showed that the description of the texture transition as a gradual rotation of the grains from the orientation characteristic of the copper texture to the {110}(112) texture of brass2 was inconsistent with the data. Instead, the data suggested that the texture within the transition region could be described as a simple mixture of the two terminal textures.5 Unfortunately, it was difficult to establish this point conclusively because of the inadequacy of corrections for the composition dependence of the single-crystal elastic constants. Since a rigorous establishment of the nature of this texture transition is essential to our understanding of the formation of rolling textures in fee metals, it is clearly important to undertake an investigation in which the composition dependence of the elastic constants would not enter. A suitable composition-independent texture transition is provided by the well-established variation in the rolling texture of copper with rolling temperature. This temperature-dependent texture transformation has been studied by smallman&apos; in several fee alloys and by Müller5 and others"&apos; in copper. They observed that the texture characteristic of copper rolled at room temperature changed to a brass-type texture when the rolling temperature was lowered to 77°K. Although it is not possible to decide unequivocally from the published pole figures whether or not the 77°K rolling texture of copper is entirely of the brass type,&apos; this complication does not affect the main purpose of the present investigation. In addition to establishing the nature of the texture within the transition region, the modulus data should also provide a determination of the temperature at which the transition occurs as well as the temperature range over which the transition extends. This information when combined with the modulus data on Cu-Zn alloys would then provide a considerable body of new information on textures in fee metals. Since these modulus results and the data obtained from pole-figure studies must be internally consistent, it is appropriate to compile a brief summary of the experimental observations based on all available methods rather than on the pole-figure data alone as has been done in the past. The primary purpose of such a summary would be to yield a more precise definition of the experimental facts on the rolling textures of fee metals, and thus greatly facilitate our evaluation of various proposed theories in this field. The final section of this paper is devoted to this compilation of consistent, experimental facts and their application to the various theories. EXPERIMENTAL PROCEDURE Two 18-lb ingots of cathode copper of 99.99 pct purity were induction-melted under a nitrogen atmosphere in a graphite crucible and chill-cast into a steel mold. The ingots were repeatedly cold-rolled and annealed (I hr at 500°C) into slabs about 1 1/8 in. thick. Blocks 3 1/4 in. wide, 2 1/4 in. long, and 1.000 in. thick were machined from each slab. The rolling schedule used was the same as in the previous investigation1 and the final thickness of the sheet was 0.050 in. with a rolling reduction of thickness of 95 pct instead of 97.5 pct as in the previous work.&apos; The compositions and temperatures of the cold baths used for the low-temperature rolling were as shown in Table I. After each pass the rolled strip was immediately immersed in the cold bath for about 1 min or until the bubbling of the bath had subsided. The modulus data were taken within 2 hr after the rolled strip was warmed to room temperature for the first time, so that effects due to recrystallization were minimized. The modulus specimens were in the shape of flat bars, 3 in. long, 4 in. wide, and 0.050 in. thick, cut with their long dimensions oriented at 15-deg intervals between the rolling direction and the transverse direction. The values of Young&apos;s modulus were deduced from measurements of the frequency at which these long narrow bars were set into longitudinal, resonant vibration as previously described.9 To excite the mechanical vibrations in the specimen, an electromagnetic drive similar to that employed by Thompson and lass" was used. The maximum in the amplitude of

Jan 1, 1968