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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

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

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By G. W. Brownell, H. T. F. Lundberg, R. W. Pringle, K. I. Roulston

The rapid improvement of the airborne scintillometer and the perfection of its efficiency for counting low energy gamma radiation has made it possible to work out a technique to map in great detail the radiation pattern at the earth&apos;s surface. On such maps low radiation over certain areas appears to indicate the existence of oil accumulations, forming a pattern similar to that obtained by the geo-chemists. RADIOACTIVE analyses of samples from the surface of oil fields were carried out more than 10 years ago in Alberta by the alpha particle ioniza-tion chamber technique,&apos; but large enough tracts could not be covered in these investigations to make possible any evaluation of the method as a means of oil exploration. Considerable interest has recently been revived, however, as a result of certain striking advances which have been made in the instrumentation available -for the measurement of radioactivity. It is the object of this paper to indicate the nature of these improvements in radiation technology and then to describe the attempts that have been made to interpret the radioactive patterns obtained in the course of airborne recordings with the new instruments. Since the survey can be carried out from the air and records can be accumulated over vast areas in a short time, the result may easily lend itself to statistical treatment. Areas have been surveyed in Alberta, British Columbia, Saskatchewan, Quebec, Texas, New Mexico, Nebraska, Colorado, Utah, and Montana. Producing fields in Alberta and West Texas have been flown over several times in different directions, Fig. 1. The operations were then extended into unknown territory and drill holes were put down on the anomalies which looked promising. The results from these drillings were encouraging and have given hopes for the development of an entirely new method of oil exploration. Any large scale method for the survey of radioactive anomalies must be based on the measurement of gamma rays, as beta and alpha rays have much too short a range to be of any significance. Thus the essential improvement which has made the present stage of this work attainable is the development of new highly sensitive detectors for gamma radiation. In the past the only detectors of any consequence that were available were the ionization chamber and the geiger counter, but both of these suffer from the defect that only a small proportion of the gamma rays passing through the counter are detected, possibly 0.1 to 0.2 pct. The recent development of the scintillation counter2,3 has completely transformed the situation and has had a considerable impact on many branches of nuclear technology. The detection of alpha particles in zinc sulphide screens by visual observation of the individual scintillations which these particles produce dates back to the early spinthariscope of Rutherford and Crookes, but the combined use of an appropriate scintillating phosphor and photomultiplier tube had to await the technical development of the latter many years later. With this development came the modern era of the scintillation counter and a knowledge of phosphors which have a large light output under the bombarding action of gamma radiation. Some of these phosphors are relatively dense and are capable of stopping a large proportion of the incident gamma radiation. As the sensitive region is the whole volume of the crystal, a very high detection efficiency, 50 pct or more, can be obtained for medium energy gamma rays. Scintillation counters for geological purposes were first developed in 19494-6 in an attempt to utilize this remarkable improvement in efficiency, which has the attractive consequence that only a small portion of the normal background of the counter is due to cosmic radiation. In 1949 tests were made in northern Saskatchewan by Lundberg Explorations Ltd. with portable scintillation counters which gave excellent results in the search for uranium and served to indicate unknown uranium deposits in areas previously closely surveyed with geiger counters. Portable scintillometers (registered in Canada) are now commercially available and in regular use,&apos; and the adaptation of the instrument to radioactivity oil well logging has also been very successful.8 Initial attempts to measure radioactivity from aircraft with scintillation counters were made during this period in the same area and yielded most encouraging results. It would be appropriate to consider some specific requirements for airborne investigations. The essential problem to be met in the detection of any radioactive source is the necessity of obtaining a signal greater than the statistical fluctuations of the background counting rate for the instrument. It is possible to show that Nt>2k2 is the condition for detectability of a signal where N = average background counting rate for the detection. t = time constant of the counting rate meter, used to determine the average number of counts arriving in a certain predetermined time interval. N&apos; = average source counting rate at the detector. k = N/N&apos;, and N>>N&apos;. Sample values are given in Table I. Assume that the aircraft carrying the equipment is travelling at 120 mph, in which case it will cover 176 ft in 1 sec. Assume also, as a first approximation, that a point source target is in range when the air-

Jan 1, 1954

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson&apos;s ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK&apos; made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson&apos;s ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8&apos;9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4&apos;~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923&apos; and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

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 C. R. Barker, D. A. Summers, H. D. Keith

Introduction Historically, the presence of methane has been a problem, mainly in and around the working areas of active coal mines, and only in these areas has drainage been considered. Drainage, where practical, has been achieved through the drilling of holes forward into the coal and the surrounding strata from the working area. These holes generaly have been short in length, although where methane drainage operations around a longwall face have been undertaken, the holes have had to be longer in order to adequately drain from the center of the face into the access gate roads. In recent years, attempts have been made to degasify the coal seams in advance of mining, without disruption of the mining cycle. This is done by drilling much longer horizontal holes through the coal in advance of the working area. Under the aegis of the federal government, methods have also been developed for draining coal seams of their methane content in advance of mining, but from shafts sunk from the surface, without using the active area of the mine as the location for the drill holes. Development of methane drainage has recently been encouraged by the potential use of the drained methane as a commercial energy source, with a need, therefore, to adequately organize a collection system, separate from mining the seam for coal. This has already been successfully accomplished, for example, in the Federal No. 2 mine of Eastern Associated Coal Corp. starting in 1975 (Johns). However, whether the system gains access to the coal through horizontal drilling from a pre- existing mine or via access through a separate shaft from the surface, long horizontal holes are required to adequately tap the methane reserve. It is to this regard-the actual drilling of the horizontal holes-that this paper is directed. It will examine potential benefits that may accrue, both in conventional horizontal hole drilling from a mine site underground, and also in drilling from the surface if a high pressure water jet drill is used to drill the degasification holes. Long Hole Drilling from an Underground Site Personnel from the Bureau of Mines have recently examined methods for conventional drilling of long horizontal holes to gain access for methane drainage. They have shown that it is possible (Cervik, Fields, and Aul) to drill out some 610 m using a conventional drilling system. Three types of bit were used in the program and by alternating between a drag bit, tricone bit, and plug bit, advance rates of between 0.6-3.6 m/min were achieved. Hole diameters varied from 7.6-9.2 cm in surface tests at bit thrusts of 1360 kg. A hole was then drilled and maintained in relative alignment within the coal seam for a distance of 640 m. Thrust levels had to be lowered to between 363-680 kg across the bit. Because the loads were smaller than those used in the surface trial, advance rates in the hole were of the order of 10-38 cm/min. The thrust level was lowered since it was found that the level of the thrust controlled the inclination of the drill so that, for example, a thrust of 363 kg caused the hole to incline downward, while at greater than 544 kg the hole inclined upward with the 9-cm-diam bit. Thrust levels increased 227 kg when the hole diameter was raised to 9.2 cm, although in such a case penetration rates in excess of 56 cm/min could be achieved. Horizontal Water Jet Drilling of Coal The University of Missouri-Rolla has recently undertaken research for Sandia Laboratories on the use of high pressure water jets as a means of drilling through coal. The initial experiment in this program called for drilling a hole horizontally into a coal seam from the side of a strip pit using water jets as the cutting mechanism. A very simple setup [(Fig. 1)] was used in this program and a 15-m hole was drilled at an approximate drilling speed of 1.2 m/min. The nozzle was designed so that the hole dimension was approximately 15 cm across [(Fig 2)] and the thrust was maintained at levels below 91 kg in moving the drill into the coal face. The system used was very crude and comprised a high pressure water jet drill enclosed within a 5.7-cm outer diameter galvanized water pipe to provide rigidity to the drilling system. This pipe sufficed to maintain hole alignment over the 15-m increment. While it is premature to make long-term predictions on ultimate applicability of this sytem to long hole drilling, certain inherent advantages of water jets can be delineated from research results and suggest considerable advantage to further research in development of this application. High pressure water was supplied at approximately 62 046 kPa from a 112-kW high pressure pump, with a 83 L/m flow through the supply line to the nozzle. The drilling system consisted of a nozzle rigidly attached to the front end of the galvanized piping. High pressure fluid was supplied to this nozzle through a flexible high pressure hose that fed from the nozzle back through the galvanized pipe to a rotary coupling attached

Jan 1, 1981

By R. Maddin

IN analyzing the relation between the orientation of new grains and that of the deformed matrix of axially extended and recrystallized single crystals of face-centered cubic metals, a two-stage rotation process" is generally used where the first rotation is made in order to account for an "adjustment of orientation to the environment of strain."&apos; It has been argued that in spite of the difference of orientation, which may amount to as much as 12" (in a brass),&apos; between the octahedral plane as observed in the parent lattice and in the recrystallized grain, it is believed to be a common plane in the sense that it constituted the nucleus in the parent strained crystal from which the new grain grew.&apos; A possible source of the deviation in orientations of a common pole in the new grain and that of the deformed single crystal matrix from which it has grown may be found in the distribution of strain resulting from the plastic deformation. It might be expected in view of the incongruent nature of shear&apos; that the perfection of the octahedral plane along which glide has occurred is disrupted and that this disruption constitutes the strain from which nuclei of new grains can grow during recrystallization. Evidence for the existence of strain along glide planes was first detected by Taylor" in 1927 and substantiated by Collins and Mathewson&apos; in 1940. In their investigations, however, the deformed single crystalline specimens (aluminum) were cut mechanically along the glide planes followed by mechanical polishing. X-ray exposures (glancing angle) of only 8 min with filtered radiation were used. It was later shown&apos; that this type of surface preparation did not remove with all certainty the mechanically disturbed surface. It was felt that a re-investigation of this phenomenon using more refined techniques might reveal a more correct extent of the strain resulting from the deformation which might correlate the deviation of the common pole of the recrystallized grain with the acting slip plane of the matrix crystal. In accordance with these thoughts, a single crystal of a brass (70/30 nominal composition) M in. in diam x 5 in. long, tapered as in previous experiments,&apos; was extended and carefully documented with respect to elongation and shear. Disks about % in. thick paralle&apos;l to the primary slip planes were cut from the specimen by means of an etch cutter." These disks represented volumes of the specimen which had been extended 0, 5, 10, 15, and 20 pct. Copper Ka monochromatic radiation was obtained by reflecting 35,000 v copper radiation from the c-cleavage face of a pentaerythritol crystal. The monochromatic radiation was collimated and led on to the disk set at the proper 0 angle for reflection from the primary (111) planes. The monochromatic beam was aligned in a plane containing the active slip direction. Following a 10 hr exposure at the theoretical Bragg angle, the disk was reset at 0 + 1°, 0 — 1", 0 + 2", 0 — 2", etc., until no Bragg reflection was obtained. The disk was then rotated 90" about its polar axis, and the same X-ray procedure was used. The results are shown in Table I. It may be seen from the results in Table I that the plastic deformation (20 pct elongation) produces fragments of the glide plane which are rotated or tilted as much as 25 " from the normal position on a purely block slip model. In addition to the large variation in 0 angle in the slip direction, there is a variation in 0 as much as 20" in the direction at right angles to the direction of slip, i.e., <110>. In view of the results shown, it may now be argued that the strain distribution finds its origin in the incongruent nature of the slip process.&apos; The use of the two-stage rotation process seems valid in attempting to explain the relation between the orientation of recrystallized grains and the matrix from which they have grown. Acknowledgment This work was sponsored by the ONR under Contract Number N6 onr 234-21 ONR 031-383. The author would like to thank N. K. Chen for reading and correcting the manuscript. References &apos;R. Maddin, C. H. Mathewson, and W. R. Hibbard, Jr.: The Origin of Annealing Twins. Trans. AIME (1949) 185, p. 655; Journal of Metals (September 1949). &apos;J. A. Collins and C. H. Mathewson: Plastic Deformation and Recrystallization of Aluminum Single Crystals. Trans. AIME (1940) 137, p. 150. eN. K. Chen and C. H. Mathewson: Recrystallization of Aluminum Single Crystals After Plastic Extension. Unpublished. 4 C. H. Mathewson: Structural Premises of Strain Hardening and Recrystallization. Trans. A.S.M. (1944) 38. :&apos;C. H. Mathewson: Critical Shear Stress and Incongruent Shear in Plastic Deformation. Trans. Conn. Acad. of Arts and Science, (1951) 38, p. 213. "G. I. Taylor: Resistance to Shear in Metal Crystals, Cohesion and Related Problems. Faraday Soc. (1927) 121. &apos;R. Maddin and W. R. Hibbard, Jr.: Some Observations in the Structure of Alpha Brass After Cutting and Polishing. Trans. AIME (1949) 185, p. 700; Journal of Metals (October 1949). &apos;R. Maddin and W. R. Asher: Apparatus for Cutting Metals Strain-Free. Review of Scientific Instruments (1950) 21, p. 881.

Jan 1, 1953