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By Robert Maes, Robert de Strycker

The Cu-Sn-As systeM was studied in the region near the Cu-42 and (214-As binary diagrams, where reactions in the solid state appear, resulting from the decomposition of the y(Cu-Sn) phase and from the formation of the 7 phase (Cu,As). The techniques used were microscopic observation, thermal analysis by dilatometry, and X-vay diffraction. The formation of the 7 phase gives rise to a ternavy pevitectoid veaction; the decomposition of the y phase gives rise to five transitional reactions. The temperatures of almost all these reactions could be determined; in the most favorable cases , the accuracy of this determination was of 11.5-C. The 7 phase is stabilized by tin additions, the arsenic atoms being replaced by tin atoms up to 35 pct; this has allowed the preparation of pure j) phase and the confirmation, by extrapolation, of the conrposition of this compound in the Cu-As diagram. In the first part of this work, the solidification reactions in the Cu-Sn-As phase diagram were studied. In the copper corner, the structure of the alloys presented the evidence of reactions in the solid state: on the one hand, all the alloys containing the y phase of the Cu-Sn diagram showed, under the microscope, that this phase had formed different decomposition products after complete solidification; on the other hand, the appearance of the 7 phase of the Cu-As diagram necessitated the introduction of a peritectoid formation reaction. The study of the decomposition of the y phase has been done by preparing about forty alloys that were homogeneous y at high temperature. The formation of the 7 phase has been studied by means of a few alloys with a composition near the homogeneity field of this phase at room temperature. The part of the Cu-Sn phase diagram of interest for this study is represented by Fig. 1, with the phase designation which will be used in the remainder of this paper; it is drawn after Hansen and Anderko.' The Cu-As diagram has already been presented in Part I of this work; the significant features of this study are the existence of the arsenides CusAs and Cu5Asz, and the formation of a compound CUEAS, designated as the 7 phase, by a peritectoid reaction at about 325°C. EXPERIMENTAL METHODS The fundamental technique for the investigation of this part of the Cu-Sn-As constitution diagram was microscopic observation; the greatest part of the observed alloys has also been subjected to thermal analysis by dilatometry; a few selected alloys have then undergone an X-ray analysis by powder diffraction. Alloy Preparation. The alloys were prepared from the same products as in Part I of this study: cathode copper, arsenic with a purity better than 99.5, and tin with a purity of 99.98. The fusion of the ternary alloys was realized from

Jan 1, 1967

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 Morris M. Fine, Norwood B. Melcher

It is out of the question, at this time, to select any one prereduction process as superior to the others. It is apparent that several share a basic similarity and that within the groups listed in Part 1, the reduction vessel is sometimes the only significant variable. Claims as to the virtues of one machine over another are difficult to substantiate: one may be rapid, another thermally frugal. Based on published data, however, all seem to be performing adequately. It would appear that processes based on carbonized pellets are most applicable to foundry iron at low production rates. Adaptation to large scale manufacture of blast furnace hot metal or to agglomeration of fine concentrates at the mine site is much less likely.

Jan 8, 1966

PRESIDENT AND DIRECTOR SCOTT TURNER WASHINGTON, D. C. PAST PRESIDENTS AND DIRECTORS WILLIAM H. BASSETT WATERBURY, CONN. ROBERT E. TALLY JEROME, ARIZ. TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y.

Jan 1, 1932

By W. A. Tiller

The conventional techniques1 for determining the liquidus and solidus surfaces of an alloy system containing more than two components are extremely tedious to use and do not provide a complete picture of the equilibrium relations between solid and liquid alloys. These techniques are unable to yield "tie-line" information concerning solid and liquid phase equilibrium, a very important parameter in the solidification description of the liquid alloy and a very necessary parameter in the preparation of "zone-levelled" alloy crystals. The tie-line in a polycomponent system is analogous to the partition coefficient, k, in a binary system, it gives the composition of the solid, Cs, in equilibrium with a liquid of composition CL. That is, CS = kCL, where CL = [CO, c1,...Cn] denotes the concentrations of the n + 1 constituents, and k = [ko, kb ,...kon] denotes the gross partition coefficient for the elements between the two phases; thus, k is the tie-line in this system. To provide complete information concerning the two-phase equilibrium in a polycomponent system it is necessary to know both the liquidus surface and the gross partition coefficient. From these two the solidus surface is obtainable. The conventional techniques are unable to provide this information in other than a binary system so we must look elsewhere. In recent years considerable insight has been gained into the correct description of the liquid-solid transformation, 2,3 and controlled solidification experiments may now be designed to both facilitate and enhance equilibrium diagram studies. In the present paper consideration is given to two methods for obtaining the liquidus surface and the tie-lines in polycomponent systems. The methods to be described below deal with the solidification of an n + 1 constituent liquid alloy of initial composition [co, Co ,...Con], where the superscripts refer to the elements present and the Oth element is considered as the solvent in which the n solutes are dissolved. The general assumptions made in the treatment are the following: (i) the solid and the liquid at their interface are in equilibrium during the growth of the solid phase, (ii) there is no diffusion in the solid phase, and (iii) the liquid phase is completely mixed and is therefore homogeneous in concentration. METHOD I In this section a general experimental method will be described which, in principle, is capable of giving an exact description of the liquidus surface and tie-lines. Consider the unidirectional solidification of the liquid alloy specimens L cm in length (freezing either horizontally or vertically). Allow the sample to be frozen very slowly from one end, as indicated in Fig. 1, with complete mixing in the liquid, and then analyze the solid bar to determine its chemical constitution as a function of position, x, along the bar. Let Fig. 2 represent a possible distribution of the ith constituent along the bar. At the point x' the concentration of the ith constituent is C1/5(x'), and the average concentration of the rest of the bar between x' and L is given by C:(X' - L) where [ A(x) c1s(x)dx c1/s(x'-L) = f A(x) dx x * and A(X) is the cross-sectional area at x. In a similar manner. all the Cf(x' - L) may be determined. Thus, the gross artition coefficient k for liquid of composition [Cs(x - L),...Cs(X' - L)] is given by -ko= CUs')/Cos(x' - L)" k0 = csn{x')/cs(x'- L) During the freezing of a charge of length L, the liquid composition may vary over a wide segment of the phase diagram and the gross partition coefficient over this segment of the phase diagram may be determined from one, bar. Fig. 3 illustrates the magnitude of Cs(g)/C,' as a function of the fraction g of the bar which has Solidified.2 We can see that the concentration in the bar will vary over a range of about 15 wt pct for C,' = 10 wt pct and k0 = 0.5. It appears that 4 or 5 specimens would be adequate to study a simple binary eutectic phase diagram.

Jan 1, 1960

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By W. Rostoker

Single isothermal sections were constructed for the titonium-rich corners of the systems Ti-Fe-O, Ti-Cr-O, and Ti-Ni-0 with a view to locating the shape and disposition of the ternary intermediate-phase fields for the compounds isomorphous with Fe3W3C. IN a previous note,' it was reported that a group of ternary intermediate phases existed which occurred in the general composition range Ti,X,O-Ti&O where X was one of the following elements: copper, nickel, cobalt, iron, or manganese. In two instances, binary intermediate phases occurred (Ti²Cu and Ti²Ni) which appeared to be isomorphous. The X-ray diffraction patterns of the phases could be indexed on a cubic lattice whose cell edge was of the order of 11 kX. Karlsson2 stated that the line extinctions and line intensities indicated that these phases were isomorphous with Fe³W³C and therefore belonged to the space group Oh. This author also noted that no unique phase of this type occurred at the composition Ti,Cr,O. This latter statement was accepted as true at the time the previous technical note was written.' However, work continued along these lines and that reported here has shown that a phase isomorphous with Fe³W³C does exist in the vicinity of the composition Ti³Cr³O but not at or near Ti4 Cr²O. The lattice parameter of this phase was found to be 13.01 kX. Metallographic examination of both as-cast and annealed specimens of these supposed ternary oxide phases disclosed structures which were far from single phase in many instances. It was considered a point of some interest to locate more positively the composition coordinates of the single-phase fields. To this end, single isothermal sections for the systems Ti-Fe-O (1000°C), Ti-Cr-0 (1000°C), and Ti-Ni-0 (900"C) were constructed. Phase relationships were studied by both X-ray diffraction and metallotrra~hic methods. Allovs were prepared as 10 g buttons by melting in a noncon-sumable electrode, water-cooled copper crucible arc-melting furnace using a helium atmosphere. Oxygen was introduced quantitatively by the use of weighed amounts of TiO² or TiO. Iodide titanium and the purest available alloying metals were used. All results are discussed in terms of the nominal composition of the melts. Previous experience with making oxygen-rich alloys had shown that oxygen losses were not significant if a homogeneous melt was produced. Weight-loss measurements were used to check loss in metallics during melting. Anneals were conducted in evacuated Vycor bulbs, and annealing times ranged from 24 hr at 1000 °C to 48 hr at 900°C. To achieve equilibrium in certain sluggish alloys, seven-day anneals were used. Debye-Scherrer powder patterns were taken in a 14 cm diam camera using filtered CuK radiation (K² = 1.541232 kX; K., = 1.53739 kX). Specimens were prepared by crushing and screening previously annealed buttons. In general, the X-ray diffraction results were used to identify the major phases, while the metallographic examinations were more useful in indicating the number of phases present. By the use of the combined results and general fundamental rules governing ternary equilibrium, it was possible to construct isothermal sections in good detail. In some instances where auxiliary lattice-parameter data were available, it was possible to lay down tie lines and to locate more positively corners of three-phase fields. Isothermal Section of the System Ti-Fe-O at 1000°C The binary systems Ti-O³ and Ti-Fe4 have been published. Binary phases, TiO, TiFe, and TiFe2, are likely to be encountered in the titanium-rich corner of the system. The structures are NaCl (Bl), CsCl (B2), and MgZn, (C14) types, respectively. Although preliminary X-ray diffraction studies indicated the presence of a ternary phase in the composition range Ti,Fe,O-TiJ?e,O, metallographic examination of two specimens at these compositions revealed the presence of other phases. Thirty-eight alloys were used to delineate the phase boundaries of the isothermal section illustrated in Fig. 1. The five almost single-phase ter-

Jan 1, 1956

By Richard L. Ashbrook, John F. Wallace

Several high-temperature eutectics of cobalt and nickel alloys were modified by small additions of selected elements. Thes-e alloys were compared to unmodified melts for microstructural variations. A few modified compositions were selected on the basis of structure and their tensile and stress-rupture behavior determined. The results of stress-rupture tests in air at 1800 F and room-temperature tensile tests of four high-temperature eutectics showed modification capable of producing substantial improvements in properties. The microstructures were altered and mechanical properties improved by: a.) dispersing a subordinate phase more uniformly throughout the matrix; b) replacing large continuous -network or platelike constituents with small equiaxed discontinuous phases; and c) by forming new, finely divided phases. tHE term "modification" is most commonly used to describe the refinement in microstructure of the Al-Si eutectic that occurs as a result of rapid cooling from the melt or on slow cooling after treatment with small amounts of sodium.1 "Modification" has also been used to describe the change from flake to spheroidal graphite in the austenite-graphite eutectic of cast iron.2 This change of graphite shape is accomplished by small additions of cerium or magnesium.3 Other systems have also been shown to be capable of modification, for example: Pb-Sn by copper;4 Al-Cu by sodium;5 Al-Mn by sodium;5 and Pb-Sb by aluminum.5 Although modification of Al-Si alloys and cast irons is usually accompanied by improved mechanical properties, a general definition of modification has been suggested to include the effect of small quantities of impurity elements on the microstructures of all eutectic alloys, regardless of the effect on the mechanical properties.6 In this paper, the term "modification" is employed in a broad sense to include the formation of third phases or even the supplanting of one of the binary eutectic phases by a third phase. The mechanism of modification, as for any solidification phenomenon, must be considered primarily in terms of nucleation and growth. Although both nuclea-tion and growth mechanisms are required to explain all the phenomena observed in connection with the solidification of modified eutectics, various investigators have usually favored one or the other.7"16 It has been shown that modification of a binary eutectic can be effected by addition of a solute element that has greatly different distribution coefficients or k values in the two phases of the eutectic. Under these conditions, differences in the temperatures at the solid-liquid interfaces of the two phases retard the growth of one phase with respect to the other.4 It has also been shown that increased undercooling favors a transition from a rodlike eutectic to a globular eutectic.17 A mechanism proposed for the transition from lamellar to rodlike eutectics depends on the concept of constitutional super cooling.18 The modification of eutectic alloys may be of interest for high-temperature service as well as at room temperature. Although "high-temperature eutectic alloys" may appear to be a contradiction in terms, many eutectic systems, including those studied in this work, have melting points in excess of 2400°F. One of the mechanisms by which high-temperature alloys are strengthened is dispersion of a relatively brittle phase such as an oxide, carbide, or an inter-metallic compound throughout a ductile matrix. For a given volume fraction of dispersed phase, strength is increased by decreasing the size and spacing of the dispersed particles.19'20 Furthermore, room-temperature ductility may also be increased by changing the shape of a brittle dispersed phase from platelike to equiaxed or spheroidal.8 Overaging and redissolving of the secondary phase limit the maximum temperature to which precipitation-hardened alloys can be used. However, in a binary eutectic system, both phases coexist up to the melting point. Although all eutectic structures are not completely stable,21 a dispersion-hardened cast high-temperature alloy might result if a fine distribution of one of the eutectic phases could be obtained during solidification. An additional reason for interest in eutectic alloys is their excellent castability.22 Since eutectic alloys, like pure metals, freeze at a single temperature rather than over a range of temperatures, their castability is superior to solid-solution alloys with long liquidus to solidus ranges. The purpose of this research was to study the effects of small solute additions on the microstructure and mechanical properties of a number of high-melting-point eutectic compositions.

Jan 1, 1967

By H. NORTON JOHNSON

THE oil industry in California during 1929 reached new heights and new depths in the discovery and development of the oil resources of the State. The discovery of new fields, and more especially the discovery and development of deeper prolific sands in known fields has, for the first time in its history, brought the potential production of completed wells within the State to over 1,000,000 bbl. oil per day. Constant improvement in equipment and technique has made possible economic development to depths unheard of but a few short years ago. Commercial production from a depth of over 4000 ft. was considered quite an accomplishment in 1923 when the Meyer sand at Santa Fe Springs was developed, and when later oil was successfully raised from this depth.

Jan 1, 1930

By J. M. GLEDHILL

(Washington Meeting, May, 1905.) A Discussion of Mr. J. M. Gledhill's paper, read by title at the Lake Superior meeting, but presented first at the New Yolk meeting of the Iron and Steel Institute (October, 1904), and here published under a mutual agreement. Between the two Institutes. Discussion. MR. E: WINDSOR RICHARDS, Past-President, said that at a recent meeting of the Institution of Mechanical Engineers a paper was read on tool steel, and he called the attention of the members to the high-speed tool steel at the Bethlehem Works. They would have the pleasure of seeing those wonderful works and would see 60, 70, 80 and 100 tons oil lathe with half-a-dozen of these high-speed tools running. PROP. H. M. HOWE (Columbia University) said that they all looked upon these high-speed tool steels as of very great importance, particularly to the machine shop. One point occurred to hire : Had it really been shown that Swedish steel is necessary, or better than equally pure steel that is not Swedish; and is cemented steel really necessary, and is there any advantage in using that, rather than equally pure open-hearth steel'! It might be well if the author could indicate the kind of evidence on which lie bases his assertion that it is necessary to have cemented Swedish steel. Many were hoping for the development of high-speed steels from elements which exist in great quantities, such as silicon, manganese and chromium, rather than from rarer metals like molybdenum, vanadium and tungsten, the supply of which is likely to be soon exhausted. If the high-cutting speed was to last more than a generation, it. seemed to him that they would have to draw upon the common ele¬ments and not upon the rare ones. MR. Tom WESTGARTH (Middlesbrough) said he fully appreci¬ated what had been said about the advantages of using high-speed steel, because great benefit had been derived from the

Mar 1, 1905

By W. G. Bearden, G. C. Howard, J. W. Spurlock

An investigation of the factors af-fec.ting the inter-zonal flow of fluids in the casing-wellbore annrc1rt.s of an oil or gas ivell is presented Laborntory tests revealed that failure of the caring-cement bond allows communi-cation of fluid at pressure differentials near 1.000 psi. Perforating with a 11011011: carrier gun does not shatter or crack the cement sufficiently to allow communication through these cracks and does not seriously affect the casing-cement bond failure pressure. The pressure to cause communication at the casing-cement bond can he increared to 3,000 psi by. limiting pipe deformation during cementing and subsequent operations. Communication can be prevented, however. up to pressures sufficient to cause the cement to fail or the casing to col-lapse, by attaching to the casing a seal ring of deformable ruhber molded between two steel flanges. When installed, one flange is attached rigidlv to the casing to serve as back-up for the gasket While tile other flange is movable. To date, these gasket seal rings have been field-tested in 27 Wells. Althotrgh communication has been noted in two wells, inter-zonal flow has been prevented in other wells in the same area by installing more seal rings between the communicaring zones. INTRODUCTION The inter-zonal flow of fluids behind casing cemented in oil wells during normal production or stimulation operations is a major operating problem. If it cccurs during production operations. it can seriously limit the pressure to which a reservoir may be depleted without harmful invasion of unwanted fluids. If it occurs during stimulation operations, it may preclude the possibility of stimulating the desired zone. This communication can be caused by failure of the bond between the casing and cement, failure of the bond between the cement and formation, or failure of the cement itself. This paper presents the results of an investigation of factors affecting com-munication at the casing-cement bond and methods which aid in preventing it. LABORATORY INVESTIGATIONS The laboratory tests performed in this study were divided into three phases. The first phase consisted of tests to determine if perforating would shatter and crack the cement sheath so severely that communication would occur through the cement itself. The second phase consisted of tests to determine more precisely the cause for the casing-cement bond failure. The third phase consisted of tests to evaluate the effectiveness of various de-formable seals attached to the casing in preventing communication. EFFECT OF PERFORATING, The effect of perforating was invest~gated in tests performed with apparatus shown on Fig. 1. Cement was poured into the annulur space hetween 5%-in. casing and 8%-in. casing and allowed to cure for 72 hours. The apparatus was then perforated with a hollow carrier gun containing eight duPont 26-A shaped charges. Bull plugs were placed over the perforations in the 8 5/8-in. casing and hydraulic pressure was applied inside the 5 1/2i-in. casing. The pressure to cause fluid communication past the cement sheath was observed and termed the "bond failure pressure". Several different cement compositions were included in these tests, the results of which are shown in Table 1. In Tests 1 through 4 of Table 1, bond failure occurred at- the inter- .

Jan 1, 1966

By C. H. Li, R. J. Stokes, T. L. Johnston

The phenomenon of solid-solution strengthening has previously been studied in a number of binary alloy systems.1-8 There has been, however, very little information published concerning the strengthening effects of specific solutes in magnesium alloys. Schmid and his coworkers9,10 investigated the behavior of aluminum and zinc in binary and ternary magnesium-alloy single crystals, but this work was done before high-purity materials were readily available. Workers at the Dow Chemical companyH reported increases in the critical resolved shear stress upon alloying magnesium single crystals with zinc and indium. Recently, Hardie and parkins* investigated the extent of hardening produced by the addition of various solutes to poly crystalline magnesium. The present work was undertaken to provide data on the strengthening effects of a number of solutes in high-purity magnesium, for the purpose of supplying further experimental information which might be useful in describing a general mechanism for solid-solution strengthening. To simplify interpretation of the results, the mode of deformation was limited to basal slip, through the use of single crystals. EXPERIMENTAL PROCEDURE Magnesium and magnesium binary-alloy single crystals containing indium, cadmium, thallium, aluminum, and zinc were prepared in the form of l/2-in.-diam rods, approximately 8 in. long, using a modified Bridgman technique in which the crystals were slowly cooled from the melt in a steep temperature gradient, in an atmosphere of helium. It was found that a solid-liquid interface travel speed of about 0.7 in. per hr consistently produced single crystals. The poly crystalline starting materials for the preparation of single crystals consisted of 1/2-in.-diam extruded rods, prealloyed to the desired composition. The unalloyed magnesium and magnesium-indium extrusions were furnished by the Dow Chemical Co. The other alloys were prepared at the Rensselaer Polytechnic Institute Metallurgical Laboratories. Some preliminary studies of the strengthening effect of indium were conducted at room temperature using a constant rate of tensile loading of 1040 g per min. Stress was applied to the crystals by means of a simple 5:l lever arm. The lever was loaded by a constant rate of flow of shot into a receptacle suspended from the long arm of the lever. Plastic flow was detected by an electrical resistance strain gage cemented to the surface of the crystal normal to the minor axis of the predicted glide ellipse. The crystals were acid machined to produce tensile specimens with a reduced section between the grip ends, with an additional step in the center of the reduced section to compensate approximately for the slip-retarding effect of the strain gage. The balance of the single crystals were extended in an Instron tensile tester. This machine employs a synchronously driven screw and automatically records applied load as a function of cross-head separation. It became unnecessary therefore, to employ a strain gage to detect deformation or to acid machine a reduced section. Preparation for testing reduced merely to chemical cleaning of the surface, thus minimizing the amount of handling and probability of accidental damage to the crystals. The rate of elongation employed in all the tests was 0.002 in. per min, corresponding to a strain rate of approximately 0.0004 per min. EXPERIMENTAL RESULTS The investigation confirmed the finding of many workers that the yield strength of hexagonal metal crystals is strongly orientation-dependent. This is illustrated in Fig. 1, in which o, the tensile stress required to produce gross plastic flow in eleven unalloyed magnesium crystals stressed at a constant rate of loading is plotted as a function of sin X, cos Ao where X, is the angle between the

Jan 1, 1960

F. E. BACHMAN, Buffalo, N. Y. (Communication to the Secretary) : The investigation so fully described by Mr. Laudig was undertaken with the idea of determining if it is possible to learn by expesiment, without an actual trial in the furnace, what economical results can be expected from the use of a given ore-mixture. The research was necessarily preliminary, and the results obtained are only to be depended upon so far as they relate to the samples treated. With the exception of the ores obtained from the stock-piles of the Buffalo Furnace Company, and several samples taken at a neighboring furnace, there is no certainty that the ores represented the average shipments of any mine. For this reason the publication of the names of the ores might do producers a great injustice. The names of the ores arc therefore withheld, and their identity is further .veiled by leaving out of the analyses the phosphorus-contents. The investigation was begun with the preconceived idea that the rate of reduction would be found to be dependent upon the accessibility of the particles of the ore to the action of the reducing-gas. In other words, a spongy, brown hematite or a very fine Mesabi would be the easiest reduced. I had formed a scale with No. 21 first, No. 30 second, No. 1 third, Nos. 5, 24, 25 and the remaining Mesabis fourth, etc , which is sufficient to show how much actual results differ from a judgment based on physical characteristics. The ore expected to be most easily reduced proved to be 25th in the list, while the one placed

Jan 1, 1897

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By C. A. Fisher

THE Salt Creek Oil Field of Wyoming occupies a unique position among the major oil fields of this country. Many years before the beginning of actual production in this area, in 1911, it had attracted country-wide attention as a district holding oil possi¬bilities. Even foreign capital, mainly French and Belgian, had sought out this district as having oil values and spent many thousands of dollars &apos;in an effort to acquire property rights&apos; in this field which was very largely located on the public domain. Owing to inadequate laws governing the acquisition of oil lands on the Federal domain and a careless practice having grown up among oil land locators of that time, a complicated title situation quickly developed in Salt Creek. This condition of uncertain titles together with the isolation of the field from industrial centers were doubtless the two most potent factors in retarding its early development. After actual production began in 1911 governmental regulations, suits between the government, and the locator, disputed ownerships between locators and claim and counterclaim continued to retard the field&apos;s development. It is believed that the title situation in the Salt Creek Field, where potential values of such magnitudes were involved, was responsible more than any other factor for the ultimate passage of the government leasing act in 1920 affecting all oil lands on the Federal domain.

Jan 1, 1925

By AIME AIME

T HE Institute of Metals Division and the Iron and Steel Division will meet jointly at the Stevens Hotel, Chicago, during the week of the American Metals Congress, Sept. 22-26. The Iron and Steel Di- vision of the American Society of Mechanical Engineers, the American Society for Steel Treating and the American Welding Society meet at the same time. but the sessions have been arranged to conflict as little as possible. A rich program of papers and plant visits has been arranged for the members and guests of the two Institute Divisions. The annual dinner and a pro- gram of entertainment are being arranged by the Woman&apos;s Auxiliary of the Chicago Section. Members are urged to register immediately up011 arrival and to make dinner and plant visit reservations at the same time.

Jan 1, 1930

By E. P. Pfleider

Important economic planning by industries, companies, financial firms and governments is predicated on estimates of future growth potential. Prior to the passage of the Taconite Amendment by the people of the State in November 1964, various admittedly conservative forecasts were made of the future of Minnesota&apos;s iron ore industry. Since that date, 3 new taconite plants are under construction, 2 are being expanded, one has just gone "on stream," and a seventh is in the design stage. These plants have a total capacity of about 35 million tons of pellets annually. The pessimism of 1964 today is being replaced by unbounded optimism. In the light of such recent developments, it becomes essential to update forecasts related to production, employment and capital investments. New projections show 50 to 58 million tons of pellet production from Minnesota by 1975. This tonnage, together with some 6 to 8 million of natural ores, should provide an annual full-time employment of 15,000 by the mining companies, plus 700 in related railroad and power producing activities and 1000 in plant construction. Total capital investment in new plants should reach $1.5 billion by 1975 and $2 billion by 1990. These current estimates indicate that the conservative goals as set in 1964 for the year 1990 should actually be achieved by 1975 or 1980. BACKGROUND Various forecasts1,2,3 have been made of the future consumption and production of iron ores within the United States. The most recent of these is by Harrison,1 delivered at the American Mining Congress meeting in Las Vegas in October. His estimates reflect the latest iron ore developments on a world wide front as well as the accelerating trend toward pellets. Minnesota&apos;s Natural Resources council prepared a detailed report in 1964 outlining the various factors that affect the future of Minnesota&apos;s iron ore industry. It presented estimates predicated on the

Jan 1, 1967

By Robert E. Green, T. Hinton

The velocities of the three possible modes of elastic-wave Propagation have been calculated for single-crystal aluminum at 1-deg intervals throughout the standard steveographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy propagation and specirzen axes are presented as arrows drawn within the standard triangle. The orientation factors associated with dislocation nzotion on the primary slip system only and also on all twelve slip systenzs have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing--7aue resonant specivnen hazle also been calculated. The relevance of these results to ultrasonic attenuation measurements is discussed. DUE to the widespread use of ultrasonics in the investigation of the properties of solids a number of authors15 have discussed in detail the theory of elastic-wave propagation in solids. In this paper the modes of wave propagation are evaluated according to the procedure suggested by reeen&apos; for the case of single-crystal aluminum at 1-deg intervals throughout the standard stereographic triangle. The wave speeds are presented in the form of contour diagrams within the standard triangle. The deviations between the direction of maximum energy propagation and the normals to the wave fronts are presented as arrows drawn within the standard triangle. The orientation-de pendent factors (orientation factors) associated with dislocation damping as derived in the preceding paper6 have been calculated for the case of aluminum at 1-deg intervals throughout the standard triangle. The orientation factors for dislocation motion on the primary slip system only and on all twelve slip systems are presented in the form of contour diagrams, for both the traveling- and the standing-wave conditions. The relevance of these results to ultrasonic attenuation measurements is discussed. ELASTIC-WAVE PROPAGATION Three waves can be propagated in a linear elastic homogeneous anisotropic medium. The velocity of propagation v of each of these waves in a medium of density p can be obtained from the determination of the eigenvalues and eigenvectors of the matrix equa- The A&apos;s are a series of moduli which are functions of the elastic constants cij and the direction cosines 1, m, and n of the specimen axis. In the case of cubic single crystals where there are only three nonzero elastic constants cll, c12, and C, the A&apos;s are, The solution of Eq. [I] will give the wave speeds (eigenvalues) and the direction cosines a, 0, and y of the particle displacements (eigenvectors). To obtain the direction of maximum energy flux requires the calculation of the energy-flux vector ET with com- w is the angular frequency, A, the amplitude, and v the velocity of the wave. The direction cosines a, b, and c of the energy flux vector are then given by

Jan 1, 1967

By George F. Weaton, Carleton C. Long, H. I. Najarian

Partial descriptions of the operation of the St. Joseph Lead Company&apos;s Joseph-town smelter have been published. In, 1936 the electrothermic production of zinc oxide was described;&apos; in 1939 appeared a description2 of the electrothermic method of producing zinc metal. Inasmuch as the plant capacity has more than doubled, and in view of the fact that operating practices have improved greatly since these publications, it seems worth while to prepare a fresh description of the present-day elec-trothermic zinc plant and practice. Josephtown smelter is situated on the south side of the Ohio River about 3 miles below its confluence with the Beaver River. In addition to river barge, the smelter is served by Pennsylvania state highway No. 18 and by a spur line of the Pittsburgh and Lake Erie Railroad (N.Y.C.). A recent extension of this spur line connects with the Pennsylvania Railroad. As originally contemplated the plant was to handle only the product of the com-pany&apos;s own mines in St. Lawrence County, New york, but owing to the incessant demand for zinc and zinc oxide, it has been necessary to supplement New York concentrates with foreign ores (principally from Quebcc and the Argentine). The general operational procedure followed comprises roasting the sulphide con-centrates, converting the sulphur dioxide into sulphuric acid, preparation of a strong-structure sinter from the calcine, crushing &lid sizing of coke, reduction of coke-sinter mixture by electrothermic means, condensation of the evolved zinc vapor to make zinc metal or burning of the zinc vapor to make zinc oxide, collection and packing of the zinc oxide. Dusts recovered by the roaster and sinter Cottrells are treated in the leach plant for separation of lead sulphate, cadmium metal and zinc sulphate. The general flowsheet is shown in Fig. I. Principal Items OF Equipment Roaster Plant Concentrate drier, 6-ft. &apos;ia. by 4O ft. 5 in., countercurrent, direct gas-fired. 3500-~on concentrate storage in three vertical steel tanks. Five modified Nichols-Herreshoff twelve-hearth roasters, 21 ft. 6 in. in diameter. Four fans for shaft-cooling air. One threedrum Stirling water-tube waste-heat boiler, 4&apos;8 hp., 200 1b. Per sq. in., with connections to upper and lower balloon flues. Direct gas-fired countercurrent rotary-kiln roaster for Cottrell dust. Necessary conveying equipment, described below. Instrumentation consists of: draft indicators, (3d hearth); various manometers; pyrometer served by thermocouples in each hearth, entrance and exit of waste-heat Joseph. entrance and exit of each hot Cottrell; roaster draft recorder and shaft air-pressure controller; temperature recorder and controller (10th and 12th hearths); SO* recorder (waste-heat boiler n

Jan 1, 1944

By AIME AIME

THE Federated American Engineering Societies through its Executive Board has endorsed House Bill 5230, introduced April 26, 1921, which provides for- the completion of the topographical survey of the United States. Before this bill can be reported out it will be necessary for the House Committee on -interstate and foreign commerce to hold hearings. This will not be done unless the engineers of the country show interest -and demand action which should be taken immediately after the recess ends and Congress reconvenes this fall. Surveys and maps have been made in this country ever since Captain John Smith mapped Chesapeake Bay about. 300 years ago, but it is only in comparatively recent years that the need for accurate maps has been keenly felt by those engaged in the industrial&apos; and commercial development of the country.

Jan 1, 1921