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Jan 9, 1951

[ ] DISCUSSION F A LORIA*-The method of testing gun steel for resistance to surface cracking described in this paper was restricted to the examination of small, rod-shaped specimens The writer would like to point out the importance of other factors in producing defects in forged and bored gun tubes which would not be apparent in this investigation because of the nature of )he test Actual section size would accentuate the possibility of internal wall (bore) defects arising from unequal expansion between the internal and external wall surfaces on firing, resulting in internal tearing Checks and tears on the inside walls arise from internal tensions and nonuniformity on cooling, but the internal tearing can be reduced by using alloys of low expansion and of good thermal conductivity so as to reduce the difference between the outer and inner wall surfaces Also, the possibility of the location of inclusion segregates within a machined gun tube becomes more likely than in a small test specimen The effect of these nonmetallics on gun life and performance is evident when one realizes that the inclusions are soft yet brittle They reduce the amount of plastic deformation which can take place before cohesive failure occurs Once localized fracture has occurred at the position of a chain of these inclusions, a sharp notch (crack) is formed which produces stress conditions more favorable to cohesive failure than to plastic deformation These cracks aid erosion by providing channelways for the explosive gases, eventually leading to the tearing out or spalling of blocks of metal Oxidation of the surface may be partly responsible for the change in the surface of gun steel during firing observed by the author The appearance of burn on the surface is an indication that high temperatures were reached on firing, resulting in a slight oxidation of the surface Since the color of the oxidized film depends on both temperature and time, a higher temperature is required for a given color to form when it is caused by explosive heat, which acts for only an extremely short time at a given spot, than when it is caused by ordinary tempering The cross section of the gun steel specimen, Fig 16, illustrates that the repeated firing temperatures were high enough to cause

Jan 1, 1948

By J. P. Pritchard, J. T. Pierce, O. G. Slay

This paper discusses the results of a technology-evaluation program to ascertain the feasibility of a piotornask-photoresist technology developed for fabrication of multiple-layer thin-film superconductive circuitry. The uehicle selected for this evaluation was a 120-bil associative data processor requiring a set of nine photomasks to define a similar number of patterned material layers of lead, tin, and polymer insulation. A total circuit area of 4 sq in. involved 2500 actitle and 12,000 passive crossings. Several short-free, electrically continuous specimens were satisfactorily completed under this program. Problems encountered in the preparation and use of the requi-ed set of Photomasks are discussed, as also are the problets of providing suitable external connections. A major retarding factor in the development of the superconducting thin-film cryotron technology for many years was the absence of batch fabrication means yielding necessary device density and count per substrate for practical applications. Early workers in the field desired only limited numbers of devices to permit careful study of discrete devices and representative circuitry integrating logic and memory capabilities. For these purposes mask stencils could be formed to selectively control the placement of materials, sequentially vapor-deposited in vacuum, to form the multilayer structure. In general a distinct pattern was required for each material layer; therefore, mechanical provisions were required to change not only the material source, but the patterning mask as well, before each deposition. All deposition steps were preferably performed in a single evacuation of the deposition chamber. Thus the means for storing, transporting, and registering masks and sources with respect to the substrate existed and were operated within the vacuum environment. In the authors' experience, the approach was and remains serviceable for preliminary device study, but was not extensible to an economical manufacturing method by virtue of the difficulties inherent in mask stencil preparation and use, and the capital investment implicit in the mechanization requirements. Since the commercial attraction of the cryotron technology stems principally from its potential for economical batch fabrication, the authors' program has placed major emphasis on fabrication methods. A highly useful method has evolved through adaptation

Jan 1, 1967

By AIME AIME

M ODERN metallurgy properly belongs to this century. The great advance made in this science is directly attributable to the discovery of the Roentgen rays. Application of the results of this discovery, together with the more recent corroborating studies in electronic diffraction have definitely and for all time established this science. Metallurgists today speak with familiarity of the atoms of the different metals in terms of their orientation, atomic volumes, lattice structures, dimensional lattice constants distance of nearest approach, and the like. One matter of profound interest, which is quite staggering to the imagination of the human mind, is the enormity of the number of atoms even in a small particle of metal. As an illustration, let us compute the number of atoms in the volume of one cubic centimeter in a single grain of absolutely pure copper. Eighteen and a fraction cubic centimeters equal the volume of one cubic inch.

Jan 1, 1940

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 ?ABBÉ, MAX F., Prest., Abbé Engineering Co, 220 Broadway, New York, N.Y. '07 ? ABBÉ, PAULO., Secy.,Abbé Engineering Co., 220 Broadway, New York, N.Y. '07 *ABBOTT, AI ARTHUR Morococlia, Peru, So. America. '95 *ABBOTT, CLARENCE Chief EDgr., Iron Mines, Dic Tennessee Caol, Iron & R. R. Co., Bessemer, Ala. '04 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94 *ABE, MASAYOSHI, Prof. of Mining, Imperial University Kyoto, Japan. '05 ? ACKER, E. O'C., Supt., Treatment Dept., Bethlehem Steel Co., So. Bethlehem, Pa. '86

Jan 1, 1910

By R. E. Allen

ONE of the most unusual oil field engineering accomplishments of the past two years is the development and rapid advance in the directed drilling of wells. Directed drilling as referred to herein is the controlled steering of the drill stem in the required direction to a given location in the oil sand. The deliberate drifting of holes is an act so far removed from what has been considered good drilling practice that all of the old questions of correlation, drillability and production difficulties are revived. Only a few years ago, during the boom days of Seminole and Santa Fe Springs, the crooked-hole problem, as it was then called, occupied a primary position among the topics of the day in the fields of California and the Mid-Continent. The net result of all the discussion and study at that time was the conclusion that oil wells should be drilled with as little deviation from

Jan 1, 1933

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By L. F. Pett

ALTHOUGH Kennecott's orebody has long been outlined, it is still necessary to define further its limits. This mine, long an advocate of churn drill methods, recently supplemented its practice by using a diamond drill. So far, the diamond drill holes have been along the main canyon floor which traverses the mine area. This zone, highly fractured, is cut by numerous friable quartz veinlets encountered within the porphyry. These veinlets, formed by filling contracted porphyry fractures with hot, siliceous, mineral-bearing solutions, are often more highly mineralized than adjacent porphyry. They pulverize on contact, yielding only slight amounts of core. For this reason neither analysis of core recovered (amounting to 37.5 pct of approximately 10,000 ft of hole drilled) nor sludge analysis considered separately would give correct assays. The following equation has been adopted: actual weight theoretical actual weight core — theoretical weight sludge Drilling is done un.der contract. Collection of core and sludge samples together with double-checked assaying is done by the company. Microscopic, specto-graphic, and X-ray examination of rock specimen saved is carried on at the University of Utah. A fund, set up by Kennecott Copper Corp. at the University, has encouraged cooperation in solution of mining research problems. The drill used is a Longyear hydraulic powered by a Waukesha 26-hp gasoline motor. A pump, Bean Royal type, is powered by a 7-hp Briggs-Stratton gasoline motor. Weight of unit is 4000 lb and is placed under tripod of 35-ft wood poles within a 25-ft sq area. The following results have been attained: Avg depth of hole drilled, ft 1215 Avg drilling depth per 8-hr shift, ft 10.11 Core Size, In. Avg depth of NC casing, ft 21 2 11/16 Avg depth of NX casing and size core, ft 178 2Ye Avg depth of BX casing and size core. ft 427 1% Avg depth of AX casing and size core, ft 585 1 5/32 Through the use of metal sludge collection boxes, 12 ft long, 18 in. wide, and varying from 12 to 24 in. in depth, sludge recovery has been maintained above 95 pct. Samples, both core and sludge, are assembled for each sample interval and averaged in 50-ft bench increments. Determinations for mineral values are made at both the mine and mill. Assay results varying in excess of 0.05 of copper assay values are rerun to determine correct assay. The organization chart for the Kennecott Utah copper mine is shown in Fig. 1. The Utah mine requires approximately four men per shovel shift to drill solid rock, properly slope banks, and trim loose material from the top of bench sections in making them safe for men and equipment working below. During recent years, while the mine has been worked day and night, powder crews have worked day shift only. Series of toe holes drilled back of advancing electric shovels comprise approximately 70 pct of all mine drilling. These holes, spaced about 21 ft apart, have a depth of 24 ft. Of the footage drilled, 25 pct is for vertical holes either 24 or 28 ft deep, spaced about 28 ft centers along the top rim of banks. This combination of toe holes, using an Ingersol-Rand DA 35 drifter mounted on a tripod and the vertical holes using an Ingersol-Rand Type X71 wagon drill is standard practice above the pit elevation. These benches are 68 ft high, with a few exceptions, while benches below the pit elevation are 50 ft high and require very little drilling other than toe holes. Five benches, varying in height from 80 to 100 ft, require a combination of toe holes plus vertical holes and bank holes or electric churn drill holes. Bank holes using the DA 35 drifter and electric churn drill using Bucyrus-Erie Model 29T, account for 5 pct of feet drilled. Until the past year, drilling of fill material on upper levels was accomplished by churn drill method. Wagon drills are now used for fills because they can be set up and drill a hole an hour. It is necessary to run an air drill 7 hr for each 8-hr shovel shift. Average drilling rates during the past year were as follows: DA 35 drifter using 2 and 3-man crews — 4.36 ft per man hr X 71 wagon drill using 2-man crews — 6.45 ft per man hr DA 35 drifter bank holes, 3-man crews — 2.53 ft per man hr Bucyrus-Erie churn drill, 2-man crews —1.9 ft per man hr Total mine avg — 4.57 ft per man hr Mine practice assigns powdermen to job locations where they perform all drilling and blasting work within the area. Almost as much labor is consumed in springing and loading holes as in drilling them. Average powder consumption is approximately as follows: Per Electric Shovel Shift, Lb To spring and chamber holes — 50 Blasting — 500 Trim banks — 50 One fifth of all powder used is Hercules hercomite bag powder while four fifths is Hercules gelamite 65 pct strength in 1 Vi in. x 8 in. sticks. Frozen material, overhanging from top banks, creates a winter hazard to shovel operators and equipment. Experiments are being conducted with a high-speed Hercules powder in an effort to eliminate this condition. Banks are trimmed by powdermen who lodge 8 or 10 bundles of powder, containing 15 or 20 sticks each, across the upper surfaces of each working face. To each bundle of powder is attached a primer with 6-ft fuse which is lighted as the powdermen, who have lowered themselves down the bank on ropes, ascend to safety. Three angle dozers, D8 caterpillars, make grades and move supplies for the average 31 drilling machines working daily. Compressed air is furnished by three Ingersol-Rand compressors, each with rated capacity of 3750 cu ft of air per min at 100 lb reservoir pressure.

Jan 1, 1952

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana' good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker's procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By George Smith

THE discussion of production control at the Insti-tute's annual meeting was profitable in that it started some thinking. One pertinent question there raised was how the opening of new mines, whose now unneeded output would inevitably react on prices, could be postponed until the market was ready to ab-sorb their output. In transportation some restraint is being exercised on building new and unneeded fa-cilities, but in production no general solution of the problem has been offered. Yet in a special field of new development of increasing importance a quick and easy solution has been suggested. I refer to the leasing of mineral deposits on the public domain. The report of the United States Coal Commission says: "In its possession of approximately 60,000,000 acres of public coal lands the Federal Government has its own responsibility in restraining overdevelopment. The Department of the Interior, which has control of these lands under the leasing law, construes the law as giving the department no discretionary right to refuse applications for leases regularly made by qualified citizens or corporations for coal deposits on the pub-lic domain. It presumes, that the applicant believes there is a need for an additional coal mine in his local-ity and expects to find a market for the coal produced. Overdevelopment, however, is a fact in the West as well as in the East, and wherever present involves needless investment and excessive costs of operation. Plainly, the leasing law should be so amended as to give the executive department full discretion in its approval of the opening of a new coal mine on the, public domain, making that approval contingent on the showing that the new mine would serve the in-terest of the consuming public." A similar view of the Federal Government's re-sponsibility in restraining overdevelopment of its oil lands has been presented by the Federal Oil Conser-vation Board. The leasing law vests little or no dis-cretion in the Secretary of the Interior, who must grant a lease to a qualified applicant regardless of any obvious country-wide condition of surplus produc-tion. This wide-open invitation to exploit and dissi-pate the people's own oil resources could be restricted by simple legislation, although as remarked by the board, such a legislative remedy for a plain economic ailment "does not evoke popular support when its purpose is avowedly to put the brakes on development of natural resources."

Jan 5, 1928

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.' These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,' one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z' alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By C. Chamberlain

The Telfer Project, Australia's newest, largest, and most remote gold mine treats 480 kt of ore grading 9.33 g/t derived from open pit mining operations. Coarse gold is recovered by gravity concentration with jigs and further upgraded wing a continuous strake launder table, and by amalgamation. Remaining gold is recovered in a cyanide circuit and incorporates flat bottom air agitators, counter current decantation (CCD) and stellar filters for clarification and precipitate removal. Overall recovery into a bullion averages 98%. The mill incorporates a number of design features that allow for maximum efficiency and security wing a minimum number of operation personnel.

Jan 1, 1983

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By Homer Turner

THE nature and comparative features of anthracite and bituminous coals have been discussed by the writer in two previous papers.1 Although this paper is offered as a further contribution to the subject, it seems desirable at the outset to repeat some of the descriptive matter of the early works in order to show the actual connection between various constituents of both coals and the new photomicrographs and other physical and chemical properties.

Jan 1, 1929

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

DAVID COLE, El Paso, Tex. (communication to the Secretary*).-I notice that Mr. Callow takes issue with me on certain points I have previously contributed to the Transactions, to which I would reply," follows: Regarding Inspiration: Mr. Callow's refinements of gravity methods made just prior to the advent of flotation in the Southwest were intended to be "down to the minute," and the gravity flow sheet for Inspiration ores which he brought out at that time as the result of his long campaign of experimentation was regarded by many as the last word in wet gravity work. It was not my intention to discredit this good work when I said "he threw small light on slime treatment." "Minus 200 mesh," however, is not-synonymous with "real slime." Repeated treatments by gravity methods will result in the separation of a very large percentage of the fine granular sulphides in sizes much finer than 200 mesh, and I gave him due credit for that. The unavoidable losses were made in the "real" slime which I mentioned in the paragraph which Mr. Callow refers to as my "statements on page 1871," and his refinements were not a solution to the real slime problem. Mr. Callow has called attention to the fact that his best results at. Inspiration in gravity work were obtained on Joe Bush ore and he presents a table, viz., Tests Nos. 68, 71, and 72; and asks us to consider and compare these results, made by his refined gravity methods, with the results obtained by 'flotation methods in the new mill "during the second half of 1915 and in August, 1916." Of course, the ore treated in the mill was what happened to come. It was not Joe Bush ore, and therefore comparisons of detail figures are of no value. In regard to Mr. Callow's statements under the caption "Callow Cells Adopted by Arizona Copper Company," I would say that those who have been sufficiently interested to read my paper and' his remarks will notice what amounts to contradictory statements on several points which I cannot allow to go unchallenged. I was on the ground constantly and got my information at first hand. The tables published were the official ones. Mr. Callow was not present during the period and has been laboring under that disadvantage.

Jan 5, 1917