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By J. H. Mallery, J. H. Keeler

THE crystal structure of Zral, the compound richest in zirconium (91.03 pct Zr by weight) in the system Zr-Al, has been found to be ordered face-centered-cubic. This compound is of particular interest, since it is encountered as the precipitated phase in potentially useful zirconium-rich alloys. It forms peritectoidally from body-centered-cubic zirconium and Zr,Al at about 975°C. The Zr-A1 constitution diagram has been reported by McPherson and Hansen.' For the primary determination a 100 g ingot was prepared by arc-melting in a water-cooled copper crucible under purified argon. The raw materials were crystal-bar zirconium (a purity of better than 99.7 pct) and spectroscopically pure aluminum. The ingot was double melted, examined metallographi-cally, and found to be quite uniform as shown in Fig. 1. The hardness of the as-cast button was VHN 390 to 445. A 20 mil diam specimen was prepared from annealed (900°C) filings of Zr,Al. The specimen was mounted in a 5 cm radius powder camera and an 8 hr exposure was taken using copper radiation with a nickel filter. The structure of the compound Zral was found to be ordered face-centered-cubic of the Cuau type, with an a,, value of 4.37220.003A. Its calculated density is 5.976e0.013 g per cu cm. The relative intensities for the lines were calculated using the formula 1+cos2 20 I oc----------------- • p • /F7 sin2 0 cos 0 1 + COS' 20 where----------------is the Lorentz polarization fac- sin2 0 cos 0 tor, p is the multiplicity factor, and F is the structure factor. The X-ray data are given in Table I. The compound has exhibited plasticity when present as particles in a matrix of a zirconium. During hot working at about 900°C, the compound has been found to deform plastically to the extent that some of the particles exhibit a length-to-width ratio greater than 4:1 as shown in Fig. 2. In answer to the discussion of ref. 1, McPherson and Hansen pointed out that the compound may be cold rolled and reduced as much as 33 pct. Zr,Al has also been found2 under certain conditions to precipitate in lamellar form at grain boundaries of the a phase of hexagonal-close-packed zirconium. Acknowledgment This work was carried out under Contract W-31-109-Eng 52 for the United States Atomic Energy Commission.

Jan 1, 1956

By H. F. Seifert

THE classification and preparation of non-ferrous scrap metals is a subject of interest to every individual and corporation that employs in its processes of manufacture non-ferrous metals and alloys and accumulates in such manufacture scrap from these materials for disposition in the form of turnings, borings, short ends, punchings, clippings, grindings, washings, etc. All too frequently the disposition of such scrap is left to individuals who have no knowledge of the subject either from a metallurgical or a commercial standpoint, or both. Much money is thus lost which with a little more intelligent effort might be saved, and in this day of fierce competition and small profits such an opportunity cannot be ignored. The Mineral Resources of the United States for the year 1925, the latest issue available (Part 1, page 221), gives the secondary non-ferrous metals of certain classes recovered in the United States for the year 1924 to 1925 as shown in Table 1. The figures are tabulated simply to give the reader some idea of the scope of the secondary non-ferrous metal industry. Approximately 900,000 tons of an annual value of $244,000,000 were recovered in the year cited. In 1916 (again using the Mineral Resources of the United States as authority) the tonnage reclaimed was approximately 632,000 tons and the value, because of the high prices for metals prevailing at that time, amounted to $265,000,000. It is not the purpose of this paper to discuss smelting and refining operations or the feasibility of an organization, primarily engaged in some other activity, conducting smelting and refining operations to convert its own non-ferrous scrap metals and alloys. The classification and preparation of these non-ferrous materials is a preliminary step, regardless of what subsequent operations the material may pass through or where these operations may be conducted. For that reason the subject can be readily discussed without any reference to subsequent activities. Space must be provided, with suitable handling facilities, scales and the necessary storage bins where the material may be accumulated. The scope of the activity, the nature of the industry and the tonnage handled will determine, in a large measure, what preparation, if any, it may be desirable to give these scrap materials to put them in the best marketable condition. By preparation is meant largely what, for the want of a

Jan 1, 1928

By J. F. Smith

ELASTIC constants of yttrium and eleven of the rare earth elements have been measured. This has been accomplished by measuring the propagation velocities of ultrasonic pulses. The velocity measurements were made by noting the elapsed time between an applied pulse and the appearance of successive echoes. The pulse-echo technique has become relatively common, and the basis of the measurement is outlined in several standard tests, e.g., Heuter and Bolt.1 Two important assumptions are made when using this method for the determination of elastic moduli. First, the pulse is assumed to propagate as a plane wave. To justify this assumption, the cross section of the test specimen should be large compared to the wave length of the transmitted pulse. For these measurements on the rare earth elements the minimum cross section wave length ratio was about 20. A second assumption which must be made when using polycrystalline specimens is that the grains are sufficiently numerous and randomly oriented so that the specimen may be approximated as elasti-cally isotopic. The grain size in the as-cast specimens which were used is believed to be sufficiently fine for this approximation, and the degree of preferred orientation is believed to be small. Supporting this viewpoint is the fact that elasticity measurements by the pulse-echo technique on as-cast specimens of other metals give results which are in satisfactory agreement with values obtained by other techniques. Hence, it is believed that the measured elasticity values for the rare earth elements are not apt to be seriously in error due to the assumption of elastic isotopy. The apparatus used in this determination was a modified Sperry Reflectoscope with a precisely calibrated time base circuit. Piezoelectric transducers were used both to generate the pulse and to detect the echoes. X-cut quartz crystals were used for the longitudinal modes, and Y-cut quartz crystals were used for the shear modes. Frequencies of 2.25 and 5 megacycles per sec were employed. Most of the specimens were 2.5 to 5.0 cm in length. Results Table I is a tabulation of the measured propagation velocities of longitudinal waves and of shear waves, together with densities obtained by Sped- ding, Daane, and Herrmann2 from lattice parameter measurements. The shear modulus, Poisson's ratio, and Young's modulus were calculated from the data in Table I through use of the following relationships: µ = pv32 [1] s=2-(vb/vs)2/2[1-(vb/vs)2] [2] and Y= 2µ(l+s) [3] where s is the shear modulus, Y is the Young's modulus, s is Poisson's ratio, p is the density, V0 is the longitudinal wave velocity, and v, is the shear wave velocity. The calculated quantities are shown in Table 11. Compressibility values can be computed from the relationship and the computed values may be compared with measured values obtained by Bridgman.8 Table III lists the data for such a comparison. The agreement is satisfactory, being particularly good for neodymi- um and gadolinium, poor for samarium, and intermediate for the other elements. Some variation is expected since Bridgman's measurements are isothermal, whereas the present measurements are adiabatic. In addition there may be some effect due to small variations in purity. Though most of the rare earth metals measured by Bridgman and all of the metals used in the present measurements were prepared at this laboratory, minor purity variations might exist since the samples came from different lots. Also, any imperfections such as dislocations, vacancies, voids, grain boundaries, microcracks, etc., should contribute to the volume change of a com-

Jan 1, 1958

By Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.' This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2'6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7'9 These effects were observed at testing temperatures in the range 100 to 300'. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.' These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180' was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio 'c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962

By A. G. Metcalfe, A. Siede

The hardening of annealed copper during fatigue testing appears to be independent of the applied stress and to occur largely within the first 4000 cycles. Copper hardened by fatigue is more resistant to annealing than copper hardened by static means, and softens by a multistage process. Creep studies at 300°C show that copper hardened by fatigue also has greater resistance to creep than statically hardened copper. Some theoretical explanations are discussed. RECENT interest in the behavior of metals subjected to fatigue stems from observations of phenomena which could not be explained by current theories of the structure of metals. In 1953 Bullen et al.l showed that the hardening caused by fatigue at low stresses did not cause severe bending of the lattice as did hardening by static methods. This was later confirmed by Wood, 'and Broom and Ham.3 Clarebrough et al4 showed that as the stress level used in fatigue hardening was increased, bending of the lattice was introduced, eventually approaching that of metals deformed by conventional cold-working methods. The type of hardening introduced by fatigue has other interesting characteristics. Kemsley5 showed that copper fractured by fatigue at low stresses resisted annealing as compared to copper hardened an equal amount by static means. The work of Clarebrough etal, shows that the manner of energy release during annealing differs for fatigue-hardened and statically hardened metal in both magnitude and temperature range of release. In addition to hardening of the lattice, fatigue has been shown to cause softening in materials previously hardened by static methods,5 and also in age-hardened alloys.7 The superposition of a small fatigue stress on the static loading of high-temperature alloys has been shown to increase their resistance to creep.' The present work was an attempt to determine the relationship between fatigue hardening, resistance to annealing, and the creep properties of pure copper. EXPERIMENTAL PROGRAM The program described here was designed to answer three questions: 1) Can stress-cycle combinations well below the failure values give significant increases in hardness? 2) Does hardening, under different stress-cycle combinations, give increase resistance to annealing? And if so— 3) Does superior resistance to annealing confer superior creep properties over statically hardened material? Three-quarter hard OFHC copper was annealed in vacuo at 550°C for 1 hr to produce a strain-free material having a fine grain size and uniform hardness. (The standard deviation of the mean hardness of the annealed samples was less than + 1.9 Dpn). Annealing was performed after machining the fatigue specimens so as to avoid work-hardened surfaces. Jigs were used to avoid distortion. The fatigue properties of the annealed copper were determined using an accurately aligned Baldwin-Sonntag SF1-U machine operating at 1800 cycles per min. This limited the minimum number of cycles which could be examined to about 4000 stress reversals. Since failure resulted in specimen damage, hardness increase with number of cycles was measured by testing specimens fatigued to different fractions of the failure values. The results are shown in Fig. 1, and are superimposed on the S-N curve of the copper in Fig. 2. The resistance to annealing of fatigue-hardened material was compared to that of material hardened by uniaxial tensile straining. Specimens hardened to equal values by both methods were progressively annealed for 1 hr at temperature in vacuo. After each annealing treatment the hardness was measured using a Leitz Durimet hardness tester with a 500-g load. At least five tests were made for each hardness determination. The standard deviation for individual specimens varied from 0.26 to 1.48 hardness points. The results are shown in Figs. 3 to 5. The discontinuous nature of the annealing process has been brought out by drawing idealized curves through the data points. This can be justified by the consistency of the results as well as by general agreement with results of Kemsley.5 The creep resistance of fatigue-hardened and

Jan 1, 1960

By S. D. Dahlgren

ORDERED G.P. zones having the cesium chloride structure were found to exist in the bcc iron-rich grains of an Fe-Au-Cu alloy that had been supersaturated with approximately equal atomic percentages of gold and copper, and aged at 400° and 350°C. Streaks and superlattice spots in electron diffraction patterns revealed the presence of the ordered zones in the aged material. The ordered Ll2 structure is commonly found for precipitates in fcc metals (e.g., Ni3A1 in nickelL7') but it is uncommon to find precipitates in bcc metals having the cesium chloride structure. The formation of the G.P. zones caused age hardening of the grains. Samples containing 3.8 at. pct each of gold and copper (with the remainder being iron) were annealed at 95@ or 1125°C in quartz capsules and were quenched by breaking the capsules under water. X-ray diffraction patterns revealed two solid solutions in the quenched samples. One solid solution was bcc and the other was fcc. The microstructure consisted of iron-rich grains of 0.3 mm diam surrounded by a yellow gold-copper-rich grain boundary network. The Au-Cu phase diagram %hows continuous solid solubility of gold and copper with ordered phases forming below 410°C. None of the ordered Au-Cu phases have the cesium chloride structure. Both Fe-Au and Fe-Cu phase diagrams3 show extended miscibility gaps and only terminal solid-solution phases. Consequently, it is reasonably certain the iron-rich grains consisted of an a-phase terminal solid solution, and the grain boundary network consisted of a gold-copper-rich terminal solid solution. Lattice parameters of the quenched solid solutions were consistent with the suggestion that the quenched phases were terminal solutions. The lattice parameter of the bcc phase (2.879A) obtained upon quenching from 950°C was higher than that (2.866A) for pure iron. The fcc phase in this sample had a lower lattice parameter than that for a 50 at. pct Au and 50 at. pci Cu solid solution, i.e., 3.866 compared to 3.877A. The lattice parameter for the 50 pct Au and 50 pct Cu solid solution was interpolated from data for Cu-Au solid solutions.4 More gold and copper were soluble in iron at 1125°C than at 950°C as indicated by a 0.012A increase in the bcc lattice parameter for a sample quenched from 1125°C. After the alloy had been quenched from 950° and 1125°C, the bcc lattice parameters were 2.879 and 2.891A1 respectively G.P. zones having the cesium chloride structure-which formed during low-temperature aging—were detected by electron diffraction and observed with electron transmission microscopy. In Fig. 1, the asymmetrical streaks parallel to ( 100) directions indicate that platelike G.P. zones had formed parallel to (100) planes of the matrix. The direction of streak asymmetry shows that the bcc unit cell of the G.P. zones was larger than the bcc cell of the matrix. The ordered cesium chloride structure is indicated by low-intensity superlattice spots at 010 positions which are nonallowed for bcc structures. The superlattice spots are streaked; therefore they are from the G.P. zones and are not caused by rel-rod effects of a thin matrix phase. The appearance and size of the zones observed in electron transmission microscopy and the appearance of the asymmetrical streaks in the electron diffraction patterns for the Fe-Au-Cu alloy were the same as those observed for a similarly treated Fe-Au alloy.' Ordered G.P. zones were detected also for an Fe-Au-Cu sample aged only at 400°C. The production of the ordered cesium chloride structure zones by low-temperature aging of super-

Jan 1, 1968

By L. H. Lange

It is the author's opinion, based on many field experiences over several years, that it is usually better to design a rougher flotation circuit with long rows of rougher cells for high tonnage capacity for maximum recovery and better operating efficiency than the alternative of a greater number of shorter rows with proportionately less tonnage of feed per row. Recent plant studies and tests in the 12,000 ton per day flotation plant of the Atlas Consolidated Mining and Development Corp., Cebu, P. I., have given further substantial support to this opinion. There are two flotation sections in this concentrator: 1) Section 1, treating half the tonnage to the total mill, has eight rows of rougher cells, each row containing 360 cu ft of cell volume. Accordingly, each row of cells receives, on the average, 750 tons per 24 hours which assays about 0.65 to 0.75% copper. The main copper mineral is chalcopyrite with minor

Jan 11, 1963

By W. G. Frailing, W. P. Sims

The Lakeview Pool of Kern County, California, was discovered in 1910 with the drilling of Lakeview No. 1 which blew out and produced an estimated 8,250,000 bbl of oil in 544 days of uncontrolled flow. The well has since been known as the Lakeview Gusher. Full exploitation of the pool did not take place until about 25 years later. A total of 112 producing wells were completed in the Lakeview sand through April 30, 1949. As of that date, about 30 per cent of the total wells drilled were still producing, with an average pool production rate of approximately 2000 bbl per day. The cumulative oil production was about 41 million bbl of oil, or 55.3 per cent of the tank oil originally in place. The pool is bordered on its down-structure side by a body of inactive edgewater and water production where present has been principally the result of coning. Since the depletion of the greater portion of the gas energy by the Lake-view Gusher, the pool has operated under gravity drive. Relatively high angle dips, good permeabilities and favorable fluid characteristics have made gravity drainage particularly effective. Since January, 1942, the oil recovery -has been relatively constant at about 53,000 bbl per ft drop in fluid level. Correlations between the volume of reservoir space drained and the cumulative oil produced indicate that an ultimate recovery of 63.3 per cent of the tank oil originally in place is attainable. INTRODUCTION The Lakeview Pool is an outstanding example of gravity drainage. It is one of many productive reservoirs of the Midway-Sunset Field, and is located in Kern County, approximately five miles southeast of Taft and two miles north of Maricopa, California. Its position rel- ative to surrounding pools and to the Thirty-Five anticline is shown on Fig. 1. The northern portion of the pool lies in sections 32 and 33, Township 32 South, Range 24 East, Mt. Diablo Base and Meridian, while the southern portion lies in sections 25, 26, 35 and 36, Township 12 North, Range 24 West, San Bernardino Base and Meridian. As no two sections bear the same number, they will hereafter be referred to by section number alone. The purpose of this paper is to review the performance of the Lakeview Pool in an effort to evaluate the effectiveness of gravity drive as a recovery mechanism. REGIONAL STRATIGRAPHY AND STRUCTURE The oustanding structural feature is this area is the Thirty-Five anticline, the axis of which plunges South 75" East through the center of Section 35. As shown on Fig. 2, the following zones are oil and gas bearing in the Thirty-Five anticline area: Pleistocene Basal Tulare Tar Sands Pliocene San Joaquin Mya Sands Top Oil or Scalez Zone Etchegoin Kinsey Sand Wilhelm Zone Gusher Sand Calitroleum Sand Miocene Reef Ridge Lakeview Sand Sub-Lakeview Miocene Sands Monarch Sands or fractured shale equivalent Maricopa Webster Sand or fractured shale equivalent Fractured Shale-Uvigerina Zone C Obispo Sand and fractured shale equivalent Pacific Shale Zone The productive interval of the Lakeview Pool is limited to Upper Miocene and Lower Pliocene deposition. In this general area, the most prevalent type of accumulation results from stratigraphic traps or permeability pinchouts. As is the case of the Lakeview Pool, strati-graphic traps resulting from angular unconformities are present. The structure within the Miocene does not parallel that of the Etchegoin (Pliocene), as the Miocene beds were folded, and in places faulted, and subjected to erosion prior to Pliocene deposition. The Lakeview horizon consists of truncated sands which occur on the northeast flank of the Thirty-Five anticline. The direction of strike is west and northwesterly through sections 25 and 36 and continues northwesterly through sections 26 and 33, to the approximate center of section 32. At this point the strike swings to the northeast and the horizon re-enters section 33. in the northwest corner. The change in strike in section 32 affords synclinal accumulation at that point. The Lake-view sand is truncated updip by the Etchegoin overlap. To the southeast, the sand shales out, while to the northwest, the productive interval appears to be limited by a combination of stratigraphic pinchout and permeability barrier. Structurally, the Lakeview reservoir presents three areas of interest, as shown on Fig. 3. Area I in section 32 is a region in which a productive Sub-Lakeview Miocene sand is present. It occurs from 10 feet to 30 feet below the base of the Lakeview sand and attains a maximum thickness of 25 feet in Well No. 21, section 32. The producing characteristics of the Sub-Lakeview Miocene sand differ radically from those of the Lakeview sand. Water production at high structural locations and abnormally high fluid levels indicate that there was no communication with the Lakeview sand. Wells in Area I penetrated this sand and produced it in conjunction with the Lakeview sand. In Area 11, the Lakeview sand is a

Jan 1, 1950

By Ta M. Li

This article draws freely on the experiences of the engineering and operating staff of P.T. Inco and its parent firm Inco Ltd. In addition, information was derived from papers presented during the recent International Laterite Symposium, held in conjunction with the 1979 AIME Annual Meeting, New Orleans, La., February 19-21. The author wishes to acknowledge all contributors and, in particular, Roy Aitken, president and managing director, P. T. Inco.

Jan 7, 1979

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Joseph Gurland

EVERAL carbide-cobalt compositions were pre-^-5 pared for the purpose of determining the transverse rupture strength of various carbide-binder systems. The binder content was held at 10 and 37 volume pct Co, so as to be representative of low and high bjnder compositions. The carbides used, WC, Tic, TaC, CbC, VC and ZrC, were selected on the basis of availability, knowledge of their properties, and small solid solubilities in the binder metal at room temperature. The methods of preparation and carbon analysis of the carbides are summarized in Table I. The carbides with cobalt added were ball milled, pressed, and sintered. vacuum sintering was used throughout, except for the WC-Cs alloys, which were sintered in hydrogen. The sintering temperatures ranged from 2500" to 2750°F for the low binder alloys and from 2300" to 2550°F for the high binder alloys. Compositions and properties of the sintered com- pacts are presented in Table 11. For the transverse rupture strength, the average and range of the five best samples of each alloy are listed. Discrepancies between the actual and theoretical densities are attributed to carbon deficiencies in some samples. The theoretical densities were calculated by assuming mixtures of carbides of stoichiometric compositions and cobalt. Representative microstructures are shown in Figs. 1 to 6. The porosity was A-2 or better' in all alloys except those with ZrC. A grain size of about 3 p was

Jan 1, 1958

By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By H. H. Dievendorff, F. W. Hertel

The method of drilling deep wells into the earth for the recovery of oil and gas is beset with many hazards. This is especially true in the Ventura Avenue field, which has the distinction of being the hardest field in California in which to complete a deep well. The hard, shifting and squeezing formations must be penetrated to great depths in the face of tremendous gas pressures. This field presents problems that keep the operators abreast with all of the latest developments in oil-field tools and machinery and in oil-well drilling practices. Equipment must be strong, and adapted to deep-well drilling and the handling of long heavy strings of casing. High-pressure sands require the utrnost care and attention of the operators and no chances can be taken, since a serious blowout may cause the loss of a well that has cost months of labor and expense. Equipment must meet these requirements or be discarded. Although the deepest wells in the world are not in this field, nor hav:. the longest strings of casing been set, nevertheless, the consistency with which deep wells are drilled and long strings of casing are set places the Ventura Avenue field foremost, in this respect, among the oil fields of the world. The V'entura Avenue field dors claim the deepest commercial oil-producing well in the world, in the Shell Co. of California's "Edison" No. 18. This well was drilled 7015 ft. and came in flowing 3280 bhl. of oil per day. This field also claims the deepest average depth of producing wells in that its Ill producing wells average 5676 ft. in depth. Of these 111 producing wells, 50 arc 6000 ft. or deeper, and 16 are 6500 ft. or deeper. Also, of the 111 producing wells 100 arc flowing, and 11 arc pumping wells. This paper is intended to set forth the methods used in the drilling of deep wells with rotary tools and the handling of long heavy strings of casing in the Ventura Avenue field.

Jan 1, 1928

The first session of the Institute was held at the Smithsonian Institution, on Tuesday evening, February 22d. The members were welcomed to Washington and to the Smithsonian by Prof. Joseph Henry. President Holley responded to the cordial welcome of Professor Henry, and then read an introductory address on the subject of Technical Education. Following the discussion on President Holley's address the following persons, duly proposed and indorsed by the Council, were elected members and associates of the Institute : MEMBERS. Emile R. Abadie,. .. .. St. Louis, Mo. R. J. Anderson,.....Pittsburgh, Pa. Commander L. A. Beardslee,. .. Washington, D. O, Charles Bender,. .. .. New York City. Charming M. Bolton,. .. . Richmond, Va. Thomas E. Bowman,. .. . Silverton, Colorado. Calvin E. Brodhead,. .. . Bethlehem, Pa. M. L. Brosius,. .. .. . Lewistown, Pa. Harvey H. Brown,. .. .. Cleveland, Ohio. James A. Burden,.. .. . Troy, N. Y. J. P. Clemes,. .. .. . Sonora, Mexico. N. H. Cone,. .. .. . Nederland, Colorado. W. F. Durfee,.. .. . New York City. Robert Frazer, Jr.,. .. . Ashland, Pa, Joseph E. Galigher,.. .. . Bingham, Utah. William Golding,.. .. . Steel Works P. O, Pa. Samuel E. Griscom,.. .. . Pottsville, Pa. Gen. E. Burd Grubb,.. .. Beverly, N. J, Arthur R. Guerard,. .. .. Charleston, S. C. Edward Hart,.. .. .. Easton, Pa. Prof. Lewis M. Haupt,. .. . Philadelphia. E. S. Hawley,.....Buffalo, N. Y. John W. Hoffman,.. .. .. Philadelphia. Nelson P. Hulst,.. .. . Milwaukee, Wis. H. C. Humphrey,.. .. . Philadelphia. Ed. P. Jennings,.. .. .Ithaca, N. Y. B. F. Jones,......Pittsburgh, Pa.

THE first session of the Institute was held at the Smithsonian Institution, on Tuesday evening, February 22d. The members were welcomed to Washington and to the Smithsonian by Prof. Joseph Henry. President Holley responded to the cordial welcome of Professor Henry, and then read an introductory address on the subject of Technical Education. Following the discussion on President Holley's address the following persons, duly proposed and indorsed by the Council, were elected members and associates of the Institute : MEMBERS. Emile R. Abadie, - St. Louis, Ma. R. J. Anderson, - Pittsburgh, Pa. Commander L. A. Beardslee, - Washington, D. C. Charles Bender, - New York City. Channing M. Bolton, - Richmond, Va. Thomas E. Bowman, - Silverton, Colorado. Calvin E. Brodhead, - Bethlehem, Pa. M. L. Brosius, - Lewistown, Pa. Harvey H. Brown, - Cleveland, Ohio. James A. Burden, - Troy, N. Y. J. P. Clemes, - Sonora, Mexico. N. H. Cone, - Nederland, Colorado. W. F. Durfee, - New York City. Robert Frazer, Jr., - Ashland, Pa. Joseph E. Galigher, - Bingham, Utah. William Golding, - Steel Works P. O., Pa. Samuel E. Griscom, - Pottsville, Pa. Gen. E. Burd Grubb, - Beverly, N. J. Arthur R. Guerard, - Charleston, S. C. Edward Hart, - Easton, Pa. Prof. Lewis M. Haupt, - Philadelphia. . R. S. Hawley, - Buffalo, N.Y. John W. Hoffman, - Philadelphia. Nelson P. Hulst, - Milwaukee, Wis. H. C. Humphrey, - Philadelphia. Ed. P. Jennings, - Ithaca, N. Y. B. F. Jones, - Pittsburgh, Pa.

Jan 1, 1876

By M. Dubrovsky, J. W. Evans

A laboratory scale cell (approximately 50 amps current) equipped with a fluidized bed cathode was used in a study of the electrodeposition of cobalt from acidified aqueous sulfate solutions The effect of current density (in the range 0.1 to 1 amp/cm2 of diaphragm), cobalt concentration (4 8 to 100 glliter) and catholyte pH (1 35 to 6 2) on current efficiency and energy consumption were determined. Generally the current efficiency increased with increasing current density and cobalt concentration Current efficiencies were comparable to those reported in the literature for conventional electrowinning

Jan 1, 1981

By C. J. Delisio

The basic concept of tunnel boring has not changed since the late 1800's. R. Stanley of Great Britain obtained a Canadian patent as early as December 1891. Mr. Stanley's machine was a device that consisted of a rotating wheel equipped with drag-type teeth; it had a means of thrusting the cutterhead against the face or heading; it had a means of clamping or gripping the machine in its bore; it had a means of collecting and depositing the cuttings into a screw-type conveyor located near the invert of the tunnel. It even had a means of varying the speed of the forward motion of the machine to suit different hardnesses of rock encountered. This description essentially fits the latest tunnel-boring machines being built today. In short, there has been no significant advance in the basic concept in 70 to 80 years. It may well be that no significant change can be expected for some time into the future. Today's machines, while still basic in concept, offer many advances aimed at faster tunneling. Among these are 1 ) improved cutters, 2) guidance and steering devices, 3) dust-control devices, and 4) mechanisms to aid in installing tunnel supports. CUTTERS The most important part of a hard-rock tunnel borer is the cutter. If the cutter can cut the rock, it is a boring machine. If the cutter cannot cut the rock, no other part of the machine can. When Jarva, Inc. decided to build a machine, the first problem was to find a good cutter. In our search, we looked at most of the cutters on the market. We selected Reed Drilling Tools' cutter because the design of their cutter was aimed at hard-rock tunneling. We feel that they build the best cutter available and provide the best possible service to their customers. As tunnel-boring machine design advanced, the transition from drag bits to roller bits was natural because harder formations required a roller bit, and it is the goal of all mole users to bore harder formations. Roller bits

Jan 1, 1970

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß' and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß' varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By G. R. Speich

RECENT studies by Smith and Olney,1,2 Olney,3 Greifer and Salli,4 Rys etal., and Olney and smith 6 have established that graphite is the first decomposition product to format the surface of hypereutectoid plain-carbon steels when they are austenitized in a vacuum or inert atmosphere and slowly cooled. This graphite evidently forms directly from the austenite and only at the surface of the specimen. The interior of the specimen is found to be free of graphite. The graphite layer can almost completely cover the specimen surface and the rate of its formation is markedly sensitive to the orientation of the austenite. The present work was undertaken to study this phenomenon further, especially with regard to the effect of temperature and austenite orientation. The material studied in this work was a high-purity iron-carbon alloy containing 0.88 pct C, 0.005 pct Mn, 0.016 pct Si, 0.005 pct S, and 0.002 pct P. Specimens were heat-treated in a commercial hot stage modified for rapid quenching.7 This permitted direct observation of the formation of the surface graphite. A vacuum of 10"" to 10-5 mm of Hg prevented oxidation or decarburization of the specimens. Specimens were austenitized for 30 min at 1100°C and quenched to a series of lower temperatures where they were isothermally transformed. Surface graphite was observed to form at 700°, 750°, and 780°C but not at 825°, 900° or 1000°C. Since the maximum solubility of austenite for graphite is 0.88 pct C at 800°C,8 surface graphite only forms at tem-

Jan 1, 1962