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By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

VITRIOL is likewise a mineral substance from whose exhalation, according to the opinion of some, are generated and produced the elemental materials or substances which produce metals, particularly gold. It is not a fumosity from metal nor is it a thing from which metal is extracted in any manner, although it shows in certain ways that it is not entirely without metal since it produces a certain trace of it. It is a thing that has a great resemblance to alum; it has a biting substance, is sharp to the taste and pungent to the tongue, and has an astringent nature. It dissolves in water and every damp place in a short time. They say that the reason for this lies, as with every other mineral, in its poorly joined watery substances. Nor does this mean that it does not contain much earthiness; on the contrary it seems to me that there are in it five. [2.9v] different participating qualities, that is, the property of sulphur, the action of alum, the corrosion of niter or of salt, and from the metals, the properties of copper and of iron. Its ore is mined in the valleys of mountains in wild but not too rugged places. It is more a gray earth or soft dead rock than a hard stone. It always has in it some yellow and green spots or near it is some sulphur mineral, either large or small.. When it is beneath the earth it exhales a sharp and very strong foul odor of scorching similar to that of sulphur. And the waters that rise where it is are all foul, earthy, and thick, some boiling with great fumes and others without great fumes, so that they surely appear to be infernal products in many places where there is a large quantity of it. After you have excavated and sorted well the quantity you wish, the ore must be put in a heap in open airy places before the vitriol can be extracted from this soil or ore, however you wish to call it. And it is left thus exposed to the weathering of the rains, the cold, and the sun for five or six months. It must be turned several times in order to bring to the surface that which was underneath; and always when this is done it is broken small with the eye of a mattock so that it is better heated and baked throughout. When it has been brought to this point it is covered over by a shed built above it or it is carried under a hut that has already been made. Here it is left to stand for another six or eight months before it is worked.

Jan 1, 1942

By T. K. Prentice

ABSTRACTED AND REVIEWED BY E. W. DAVIS,* MEMBER A.I.M.E. THE January-February number of the Journal of the Chemical Metallurgical and Mining Society of South Africa is made up entirely of a discussion of Ball Wear in Cylindrical Mills. Following the principal paper by T. K. Prentice are several remarkably pertinent and carefully prepared discussions. Few persons in this country would be likely to see this publication, and since the information presented is new and of current interest, it seems desirable to abstract and review this publication for the benefit of the members of the A.I.M.E. The purpose of the investigation is stated in the first two paragraphs of Prentice's paper, as follows: Early in 1941, The Chamber of Mines Steel Products, Limited, initiated a series of tests under semi-working scale conditions to determine, if possible, those physical and chemical properties of a ball which make it resistant to wear when used in a cylindrical mill as a grinding medium, with the primary object of incorporating those beneficial qualities in the balls being produced at their works. This paper describes the tests carried out and discusses the results obtained. From these results it was possible to formulate a new theory relating to ball wear in cylindrical mills. This theory is presented in the second portion of this paper. PRACTICAL BALL-MILL TESTS IN A CYLINDRICAL MILL Part I of the paper begins with a discussion of the methods used for the manufacture of grinding balls in South Africa. The following paragraph is of particular interest. The cast steel ingots, 4 ¼ - in. square by 3 ft. 6 in. long, are re-heated in a gas-fired sloping stationary-hearth furnace and then rolled in a six-pass continuous mill into 2 5/8 in. round billets. Some of these billets are then removed and cut into suitable lengths for forging into 4 in., 3 ½ in., 3 in. or 2 ½ in. balls by means of three Drop and two Beché hammers, but the greater number, whilst still at about 1,000 ºC., pass directly into a set of scroll rolls which produce, in an ingenious manner, finished 3 in. balls direct from the 2 5/8 in. billets. Except in special cases, all balls are allowed to cool in the atmosphere and are not water quenched. Details of the Tests In order to enable the reader to evaluate properly the results and conclusions in the rest of the paper and in the discussions following the paper, most of the information presented by the author under this heading is quoted: ….. The testing unit was a nominal 30 in. diameter and 18 in. long centre discharge Denver Ball Mill. The ore pulp to the ball mill comprised a small portion of the normal feed to one of the fourteen City Deep 5 ft. 6 in. X 22 ft. tube mills, and the grinding media consisted of the balls under test plus other balls to give the desired load. The running time of the test-mill was divided into approximately equal periods of five days 13 ½ hours each. The usual procedure was to examine and make up the load

Jan 1, 1944

By George T. Wickes

Several years ago, Mr. Robert A. Cook described and illustrated in our Transactions a mechanical coke-drawer, patented in 1891 by Mr. Thomas Smith of the Thorncliff Iron Works, Sheffield, England, and first introduced in the United States in 1896, at the coking-plant of the Latrobe Coal Co., Latrobe,Pa. This machine has not received any very extended application in this country, although it was successfully used in two places for a number of years. The present paper describes a new and simpler machine, containing few wearing-parts, and capable of withstanding continued rough usage. Anything which tends to prolong the general use of bee-hive ovens will be welcome to those who are interested in cheapening the cost of producing coke in such ovens, especially if it provides satisfactory mechanical means, replacing the hard labor involved in drawing coke by hand with the old-fashioned " duck bill." The difficulty of finding efficient coke-drawers, especially during the summer season, and in the South, is notorious. Yet, notwithstanding the great improvements that have

Jan 1, 1906

By R. C. Croft

Many chemical methods of upgrading ilmenite to enhance its titanium dioxide content involve reduction of the FeO in this mineral followed by solution of the metallic iron produced. While the use of most mineral acids for this purpose entails acid regeneration or salt disposal problems, these difficulties can be overcome with carbonic acid. Satisfactory rates of iron removal have been achieved at temperatures below 100° C and at CO, pressures up to 600 psi. Lowering of gas pressure over soluble bicarbonate solutions permits recovery of CO. and precipitation of iron oxide. The removal of the manganese, often present in ilmenites, is also feasible with these treatments.

Jan 1, 1972

By A. J. Terrones

THE classical papers on contact metasomatic deposits by Lindgren on the Clifton-Morenci district,' by Barrell on Marysville, Mont.,' and by Gold-schmitt on the Oslo district, Norway,' laid the foundation for understanding of the importance of separating the metamorphic process from the subsequent metasomatic stage. Knopf' made a big step forward by recognizing that sulfide ore minerals are invariably younger than silicates and by further stressing the importance of structural control" in ore finding. Some years later Harrison Schmitt" fought the idea that contact metasomatic deposits are erratic, irregular, bunchy, economically marginal, and of small size, concluding that these descriptions have little factual basis. He emphasized the importance of detail mapping and careful geological study as fundamental requirements for a better understanding of these deposits. This article presents a comparative description of the structural features at the Magistral, Antamina, Morococha, Vilca, Ferrobamba, Katanga (Quibio), Tintaya, and Huarca contact deposits (Fig. 1). Further, it will describe how these structural features controlled the emplacement of the intrusives, their shape, distribution of metamorphic and metasomatic halos, and sulfide deposition in post-skarn structural channelways. Finally, the modifications introduced by a superimposed hydrothermal stage recognized at some localities will be discussed. Primary exploration and careful sampling of recognized structural targets were instrumental in outlining the copper ore potential at the Antamina and Tintaya districts, thus proving the benefits and reward of careful geological examinations in this type of deposit. The Magistral District: This district lies in the Province of Pallasca, Department of Ancash, in northern Peru, at 8o 16' S and 77" 47' W. High to medium grade copper orebodies in garnetite, bordering a quartz monzonite stock, are exposed at the bottom of a glaciated valley in the western slope of the Andes at 4250 m (14,000 ft)* elevation.

Jan 1, 1959

By Louis A. Panek

Caving of previously undisturbed ground was conducted for a period of about 20 months at two locations about 600 m (2000 ft) apart in an Arizona porphyry copper deposit. When mining was suspended the width of the mined zone at both sites was on the order of one-half the depth and the thickness of ore extracted was only a fraction of the rock column. Thus the results have potential application to predicting the subsidence above a cavern-type excavation. Break cables were used to detect the upward progress of caving. Analytical aerotriangulation was used to determine the vertical and horizontal displacements of 400-plus surface targets covering a 1585 m (5200 ft) square area. The measurements are summarized and interpreted with a view to predicting the rate of rise of a caving brow, detecting the initial surface subsidence, and characterizing the extent, the location, and the varying degrees of expected damage to surface facilities.

Jan 1, 1984

By J. W. Hickman

INTRODUCTION RECENT work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of. these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution-type over-the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions.1 In. order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where Cu+ is 0.96Å and Ni-++ is 0.70Å, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with electrons. This composition in the copper-nickel alloys corresponds to 40 at. Pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is filled at 6o at. pct copper or 4o at. pct nickel. Mott and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel -has the-configuration: 3d8 4s2 and copper: 3 d10 4s) then at 60 at. pct copper or 4o at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may' exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. SURVEY OF LITERATURE The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1948

By A. H. Lindley, Fraizer M. Stewart

For many years large mining companies were able to finance nearly all of their capital requirements from internally generated funds. However, during the last decade, funds needed for capital expenditures, dividends, and scheduled debt retirement have grown faster than cash flow. As a result the minerals industry has had to rely increasingly on other sources of funds. Getting the capital for new mining projects is a challenge, particularly for smaller companies. New methods of financing and new variations to old methods have been developed and more are needed. Commercial banks are short-term lenders. By policy their loans are limited to low risk loans-those made solely on the borrower's general credit, and secured loans where cash flow is sufficient to provide repayment within a comparatively short term. To maintain liquidity, banks prefer to make loans of less than seven years' term. If a longer loan is needed an insurance company or pension trust may take the long-term part.

Jan 1, 1971

By William Hutton Blauvelt

Coke is the product of dry distillation of bituminous coal, by which the volatile matter is driven off, producing a hard body of cellular structure. Not all bituminous coals will coke, and there has been much discussion regarding the substance which is present in coking-coals to distinguish them from dry coals. Professor Lewes says that the bituminous matter in coal is largely derived from the spores of fossil mosses. Resins are present in all soft coals, and contribute largely to the cementing of the coke. The resinates and hydrocarbons begin to distil out at moderate temperatures and leave the pitchy residual, which at 500' C. forms a mass already well caked together, if the proportion of humus residual is not too great. This coke is soft, but if the heat be raised to 1,000° C. the pitch decomposes further, leaving carbon, and Professor Lewes is convinced that the coking bond is due to these liquid products which distil off, leaving pitch, which then carbonizes and binds the mass into coke. Professor Parr concludes that the structures of the organic compouilds of the coal Which furnish the cemeding-material for coke, and which are apparently attacked by oxygen, have not been determined and seen] to vary somesvhat in different types of coal. However, they yield, on oxidation, humic acids of varying composition which decompose into powdery residues. Because of the complex nature of these substances and the difficulty experienced in isolating and identifying them, the theory of coking is still an open problem and the explanations advanced are largely hypothetical. In the coking process the volatile matter driven off in the oven consists mainly of tar, ammonia, and gas, familiarly known as by-products. Both the quality and quantity of coke and by-products vary greatly With the composition of the coal.

Jan 1, 1913

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By David Kramer, Cecil G. Rhodes

Critical transport currents were measured as a function of perpendicular external magnetic field in Ti-22 at. pct Nb wire samples. These samples were heat-treated to yield w Phase precipitates at denslties ranging from 10 to 10 17cm-3. The Precipitates are ellipsoids of revolution with major axes of 50 to 1300A. Flux-Pinning by w precipitates is responsible for the high critical transport currents that were ob- ThE ability of a type II superconductor to sustain a zero-resistance transport current (Jc) in an external magnetic field (H) is due to the presence of micro-structural features which can impede the motion of magnetic flux penetrating the superconductor under the influence of a Lorentz force. Such features are referred to as pinning sites. The pinning strength is tained. A sample cooled from 800°C and annealed 1 hr at 450°C carried a critical tramport current of 10 amp per sq cm at 30 kG. Variations in the current-carrying ability of this alloy are due to changes in its pinning strength which is a function of precipitate density and composition and of the composition of the matrix. the reaction of the bulk superconductor to the Lorentz force and depends on the efficiency of the individual pinning sites and on their volume density. The super -current density increases with pinning strength, other things being equal. The above concepts are discussed in detail in a comprehensive review by Livingston and Schadler.' In Ti-Nb alloys, as in other binary titanium alloys, the metastable hexagonal w phase usually forms below the p/a + p phase boundary near the titanium side of the phase diagram. Stiegler et a1.' have summarized much of what is known about w phase in titanium and zirconium binary alloys. The present work deals with

Jan 1, 1968

By A. A. Terchick, J. C. Anderson, D. T. King

During 1972-1973, U.S. Steel acquired an existing southern West Virginia high volatile coal mine property including a 150 tph heavy media feldspar jig preparation plant. Expansion of production from the property required an increase in plant capacity to 300 tph, replacement of the feldspar jig with a hydrocyclone circuit, and inclusion of a water clarification thickener system. The rugged and restrictive nature of the terrain adjacent to the plant facility indicated prohibitive construction costs and severe site congestion would be encountered if a conventional water clarification thickener were installed. A high-loading, small-volume thickener, developed initially for the sugar beet industry by the Enviro-Clear Co. of New York, was investigated by U.S. Steel Research for possible coal preparation application, utilizing bench scale and small scale pilot plant evaluation methods. Results of testing at existing U.S. Steel preparation plants indicated predictable successful application of the Enviro-Clear thickener, so a 35-ft-diam unit was installed. The two-phase thickener system, utilizing presettled bottom sludge as a filter-clarification media, has successfully performed since commissioning in April 1973, producing clarified water competitive with conventional thickener systems with freedom from usual thickener operational problems.

Jan 1, 1976

By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A&apos; exp(-AT). In these equations, a and b are constants which depend on temperature, A&apos; is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969

By G. Sachs, L. J. Ebert, W. F. Brown

IT is a generally recognized fact that a steel quenched from the austenitic range and tempered to yield a structure composed of tempered martensite becomes increasingly more ductile with increasing tempering temperature. However, the conventional tensile test fails to yield any value that is sensitive to differences in behavior on tempering among the various low-alloy steels or among different heats of a particular steel. The notched impact bending test, on the other hand, has been recognized for a considerable length of time as capable of revealing differences in impact properties among various steels tempered to the same strength level (i.e., the same tensile strength in a conventional tensile test), However, this test is very complex and its significance has not been clarified up to the present time. Of its three characteristic features-the high speed, the notch, and the bending-the notch has been found by Davidenkov2 to be the most potent embrittling factor. Recent investigations on low-alloy steels3,4,7,8 have shown static notch-bar tensile tests to be more lucid and to evaluate the metal properties in much the same manner as impact tests, In an attempt to analyze the fundamental nature of this test,8 it was found possible to separate the effects of the two basic characteristics of the stress pattern introduced by the presence of a circumferential notch, the stress state and the high initial stress concentration at the notch bottom, The major conclusions drawn from these previous investigations were as follows: I. The magnitude of the triaxiality at fracture depends primarily on the initial notch depth. Its effect is a great reduction in the average ductility (contraction in area at fracture in the notched section) as compared with that observed in uniaxial tension, This triaxial stress state occurs at a point in the interior of the notch specimen, It determines the notch ductility if the notch is mild and/or the metal possesses a considerable ductility. On the contrary, brittle specimens probably fracture on the metal surface (at the notch bottom) at which point biaxial stress state is present, This biaxiality also considerably reduces the ductility of the metal. For small notch ductilities the notch strength and the notch ductility become very sensitive to embrittling factors, This is contrary to the behavior of the ductility values derived from a conventional tensile test, which are comparatively insensitive.

Jan 1, 1946

By H. A. Hancock, L. M. Pidgeon

Equilibrium carbon monoxide pressures were measured over the reaction between chromium oxide and a number of solid ferrochromium alloys in the composition range 0.4 to 4.8 pct C and 0 to 49 pct Fe. Measurements were also made for the carbides Cr23C6 and Cr7C3 which agreed well with previous investigations. Between 1050°and 1400°C the pvessures varied from 0.1 to 56 mm and increased markedly with the iron and carbon contents of the alloys. The data were used to estimate the activity of carbon in the alloys and to calculate the equilibrium conditions for the decarburization of a useful range of ferrochromium alloys. WHEN ferrochromium is produced by the reduction of chromite with carbon in an electric arc furnace it invariably contains up to 10 wt pct C. For many purposes such as the production of stainless steel, it is necessary that the carbon content be as low as from 0.02 to 0.05 pct. Thus an important part of the ferrochromium industry consists of the production of low carbon ferrochromium. The classical Bessemer steelmaking technique cannot be used to oxidize low carbon contents in chromium and ferrochromium alloys without also oxidizing the chromium. Recently a new commercial process2-4 has been introduced for oxidizing carbon from high chromium content alloys which consists of heating the solid alloy with such oxidizing agents as Cr2O3, Fe2O3, or SiO2 in a retort at reduced pressures. By maintaining the carbon monoxide pressure below the equilibrium value for the system, the carbon can be removed as carbon monoxide without oxidizing the chromium. The equilibrium conditions for the decarburization of solid chromium carbon alloys have been determined by Boericke5 who measured the carbon monoxide pressure over the reaction between the various chromium carbides and chromium oxide. A typical reaction is shown below. Cr23C6 + 2Cr2O3 =u 27Cr + 6CO [1] These values are not applicable to the decarburization of commercial ferrochromium alloys which invariably contain major amounts of iron. The present investigation was therefore undertaken to measure the change in the equilibrium carbon monoxide pressure brought about by additions of iron to the Cr-C-0 system, thus extending the work of Boericke into the region of the production of low carbon ferrochromium. MATERIALS AND METHOD Materials. Measurements were made on two carbides of chromium, Cr233C6 and Cr7C3, and fifteen Fe-Cr-C alloys. The chromium carbides were made

Jan 1, 1963

By K. E. Brown, A. R. Hagedorn

Continuous, two phase flow tests have been conducted during which four liquids of widely differing viscosities were produced by means of air-lift through 1%-in. tubing in a 1,500-ft. experimental well. The purpose of these tests was to determine the effect of liquid viscosity on two-phase flowing pressure gradients. The experimental test well was equipped with two gas-lift valves and four Maihak electronic pressure transmitters as well as instruments to accurately measure the liquid production, air injection rate, temperatures, and surface pressures. The tests were conducted for liquid flow rates ranging from 30 to 1,680 BID at gas-liquid ratios from 0 to 3,-270 scf/bbl. From these data, accurate pressure-depth traverses have been constructed for a wide range of test conditions. As a result of these tests, it is concluded that viscous effects are negligible for liquid viscosities less than 12 cp, but must be taken into account when the liquid viscosity is greater than this value. A correlation based on the method proposed by Poettmann and Carpenter and extended by Fan-cher and Brown has been developed for 1¼-in. tubing, which accounts for the effects of liquid viscosity where these effects are important. INTRODUCTION Numerous attempts have been made to determine the effect of viscosity in two-phase vertical flow. Previous attempts have all utilized laboratory experimeneal models of relatively short length. One of the initial investigators of viscous effects was Uren1 with later work being done by Moore et al.2,3 and more recently by Ros.4 However, the present investigation represents the fist attempt to study the influence of liquid viscosity on the pressure gradients occurring in two-phase vertical flow through a 1¼-in., 1,500 ft vertical tube. The approach of some authors has been to assume that all vertical two-phase flow occurs in a highly turbulent manner with the result that viscous effects are negligible. This has been a logical approach since most practical oil-well flow problems have liquid flow rates and gas-liquid ratios of such magnitudes that both phases will be in turbulent flow. It has also been noted, however, that in cases where this assumption has been made, serious discrepancies occur when the resulting correlation is applied to low production wells or wells producing very viscous crudes. Both conditions suggest that perhaps viscous effects may be the cause of these discrepancies. In the first case, the increased energy losses may be due to increased slippage between the gas and liquid phases as the liquid viscosity increases. This is contrary to what one might expect from Stokes law of friction,&apos; but the same observations were made by ROS4 who attributed this behavior to the velocity distribution in the liquid as affected by the presence of the pipe wall. In the second case, the increased energy losses may be due to increased friction within the liquid itself as a result of the higher viscosities. The problem of determining the li- quid viscosity at which viscous effects becomes significant is a difficult one. Ros4 has indicated that liquid viscosity has no noticeable effect on the pressure gradient so long as it remains less than 6 cstk. Our tests have shown that viscous effects are practically negligible for liquid viscosities less than approximately 12 cp. Actually there is no single viscosity at which these effects become important. These effects are not only a function of the viscosities of the liquids and of the gas but are also a function of the velocities of the two phases. The velocities in turn are a function of the in situ gas-liquid ratio and liquid flow rate. Furthermore, the role of fluid viscosities in either slippage or friction losses will depend on the mechanism of flow of the gas and liquid, i.e., whether the flow is annular. as a mist, or as bubbles of gas through the liquid. These mechanisms are also a function of the in situ gas-liquid ratios and the flow rates. It would thus seem that the best one could hope for is to determine a transition region wherein the viscous effects may become significant for gas-liquid ratios and liquid production rates normally encountered in the field. The viscous effects might then be neglected for liquid viscosities less than those in the transition region but would have to be taken into account when higher viscosities are encountered. There are numerous instances where crude oils of high viscosity must be produced. The purpose of this study has been to evaluate the effects of liquid viscosities on twephase vertical flow by producing four liquids of widely differing viscosities through a 1 % -in. tube by means of air-lift. The approach used in this study was as follows:

Jan 1, 1965

By B. C. Riblet

THE president of a large smelting and refining company once telegraphed me that they had acquired extensive mining interests in northern Peru and requested me to inspect their properties as it would be necessary to install a system of aerial tramways between their mines and treatment plant. The concentrator was about 50 mi. from the coast, reached by a fairly good motor road. From the concentrator an aerial tramway would he required, about 6 mi. long, to their first property, a gold and silver mine. The lower terminal of the tramway was at an elevation of 4000 ft. and the mine at an elevation of 9500 ft.

Jan 1, 1937

By Eugene S. Machlin

A classical theory of solid solutions involving neavest-nergkbor intevactions with both central and linked-central forces between atoms has been developed. It has been found that the theory, where it can be checked quantitatively, is in ageement with experiment. The theory encompasses a description of many diverse pkenomena, such as antiphase shift structures, size effect, relative stabilities of various solutions, lattice para,neters, and order-disorder transitions. In particulav. a quantitative prediction not involving adjustable pavameters is made concevning the deviation of the Au-Cu interatonlic distance in long-range ordered (Ll,) Cu-Au I fronl the average distance based on the distances in pure gold and copper. This prediction, which is in agreement with expel-intent, has not been encompassed by any preuious theory. The theory of order-disorder is fragmentary. That is, no one theory exists that can explain the variety of qualitative phenomena observed. Further, many theories are not in good quantitative agreement with experiment. This subject has been reviewed by Muto and Takagi, Tuttman, and Oriani.3 There exists no doubt that the quasi-chemical approximation is not a complete description and that the inclusion of strain energy using macroscopic elasticity theory concepts leads to results in disagreement with experimenL4 The observation of antiphase domains and ordering systems such as Cu-Pt has led to Brillouin zone treat-ment of the order-disorder transition as opposed to the classical Ising model. The objective of this paper is to demonstrate that it is possible to develop a pairwise approximation model that can explain many of the observed order-disorder phenomena that have puzzled investigators in the past. This theory is based upon an empirical model due to ergmman&apos; for the elastic constants of metals. This model is generalized for multicomponent systems. As will be shown, the theory yields a short-range ordering energy for the disordered solution which differs from the ordering energy calculated from the differences in energy of disordered and long-range ordered solutions. It will be demonstrated that there is no necessary correlation between heats of formation and the tendency to order or between size effect and the tendency to order. Also, the existence of antiphase domains and iso-short-range-order systems that form superlattices (Cu-Pt) is predicted on the basis of the theory. Further, the relative stability of competing superlattices is calculable from the theory. If single-crystal elastic-moduli data are available for the pure components and one superlattice then there exists but one adjustable parameter in the calculation of lattice parameters for both the disordered and ordered solid solutions. In one special case, no adjustable parameters are required and a quantitative prediction is made. For the calculation of energies and partial order, there exists but one additional adjustable parameter, the pair-exchange energy V used in the quasi-chemical approximation (or the Ising model.) However, in these calculations, much more precise values are required for the single-crystal elastic moduli than available if the quantitative uncertainties in the predicted values of the energies are to be sufficiently small. THEORY ~er~man&apos; has developed a model with which he was able to obtain fair agreement with experiment for the relations between the elastic constants for metals. This model which we shall call Bergman&apos;s model is a linear combination of his models I and 11. In effect, Bergman, in this model, considers that each interatomic distortion is composed of two components: a classical central force distortion with an associated central force constant and what we shall call a linked-central force distortion with an associated linked central-force constant. The linked-central force distortion component obeys the constraint that the sum of such distortions over all the bonds equals zero. No constraint is imposed on the classical central force distortion component. Bergman&apos; derives the constraint on the linked-central force distortion on the basis of application of Pauling&apos;s relation between bond distortion and bond number to metals.ga This assumption is not logically necessary, however, and the Bergman model may be taken as a mathematical model for elastic constants, e.g., a purely empirical model without a physical basis. In the present work, the method of Bergman has been applied to two-component systems (solid solutions). In place of an external strain—which would allow a calculation of the elastic constants for the two-component system—it is considered that internal interatomic distortions exist as a consequence of having three potentially unequal distortion-free interatomic distances and but one "average" interatomic distance. It is assumed that the distortion-free interatomic distances between atoms of the same element are those found in the pure element having the same undistorted crystal structure as the solid solution. The distortion-free interatomic distance between unlike atoms is in general not measurable except in the probably nonexistent

Jan 1, 1967