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By W. E. Rudolph, R. E. Baylor

DUE to its location in the Atacama Desert, one of the most barren of the earth's surfaces, Chuquicamata's water supply presents unusual problems. Yearly rain-fall averages less than one tenth of an inch at the plant. However, there are summer showers above 12,000 ft in the Cordillera to the east, the resulting run-off flowing through old river valleys buried beneath more recent volcanic formations, to be impounded within sediment-filled basins. This water emerges at springs where the outlets of these basins are blocked by lava flows, and here are formed the small streams which feed the only important river of the region, the Rio Loa. Chuquicamata's water is obtained from these springs and rivulets. [ ] The map above indicates four pipe lines from which potable and industrial water are supplied. Potable water, amounting to 4500 metric tons per day, is conveyed in the Toconce pipe line from springs 59 miles due east of Chuquicamata. This water is used not only for drinking, but also for boilers and other needs requiring high quality. For industrial water at the oxide plant, there are two 12-in. pipe lines from the Rio San Pedro, carrying a total of 17,000 metric tons per day of slightly brackish water. This water is at present used mainly for leaching and for hygienic purposes. Water Source Found For the present and future needs of the sulphide plant, it was calculated that at least 32,000 metric tons per day of make-up water would be required. For this purpose, a pipe line of 44 miles length was constructed to bring in the entire flow of the Arroyo Salado, one of the eastern tributaries of the Loa. The salt content of this water is so high (over 5000 parts per million of solubles, mostly chlorides) that it is highly detrimental to farming, and the Chilean Government had been studying projects to separate these waters from others of the Loa system in order to improve agricultural conditions in the fertile valley of Calama. So it happened that the Government was willing to award rights to the Arroyo Salado waters under agreement whereby the Mining Company removes waters from the Rio Loa system above Calama for all time. The outlet of these waters, after serving their purpose at the new concentrator and leaving the plant in tailing, is the Salar de Talabre, an old salt lake which presents fully ten square miles of surface to serve as an evaporating pan, the outlets having now been blocked by dams. Here the dry climate of Chuquicamata is a favourable factor, evaporation averaging slightly above 1/4 in. per day. The Toconce and San Pedro pipe lines have been functioning from 26 to 34 years, and through the use of special cleaning tools which were developed at the plant, as well as deaeration of the more active Toconce water, these pipes are now maintained at capacities which do not diminish as years go on. Constructing the Dam The Arroyo Salado pipe line design and construction involved certain special and interesting features, and inasmuch as this line and its intake works are solely for the needs of the new sulphide plant, more detailed description is given. The waters are impounded at a gravity dam constructed of concrete to a height of 100 ft above the river bed, keyed into the precipitous Dacite walls of the narrow canyon (barely 6-ft wide at the bottom, only 25-ft width at 50 ft above). A small secondary dam was built 100 ft down stream from the main dam, providing a pool of 15-ft depth to protect the main structure from flood flows over the spill-way during the rainy season. A system of four 36-in. syphons was designed for discharging these flood waters from the lower depths of the lake, in order to avoid eventual sedimentation behind the dam. The lake has a length of 3300 ft, and its water level is controlled by an adjustable spillway permitting draw-down of eighty inches, amounting to 41,000 metric tons of available capacity. This regulation is necessary because of wide fluctuations in stream flow between day and night due to freezing of feeders. During the construction of the dam the entire river flow was handled within a 36-in. pipe line some 2000 ft in length. As the excavations proceeded

Jan 1, 1952

By W. J. Schuster

Safety in coal mines depends largely upon adequate training of the foreman. Although management must provide modern and safe equipment and at all times keep mines in first class condition from a safety viewpoint, final results will be determined by the quality of supervision. HANNA COAL CO., Division of Pittsburgh Consolidation Coal Co., operates three large underground mines in eastern Ohio. The section of Pittsburgh No. 8 coal seam in which these mines are located varies in thickness from 52 to 64 in. It is immediately overlain by a stratum of shaly material 12 to 15 in. thick locally known as draw slate, which is structurally very weak and which disintegrates rapidly upon exposure to atmosphere. Immediately above the draw slate as it is normally found is a band of extremely high ash material 6 to 12 in. thick known as roof coal or rooster coal, and above this is a stratum of conglomerate material varying from 4 to 10 ft in depth. Overlying the conglomerate is a relatively thick stratum of limestone, the first stable material above the Pittsburgh coal seam in eastern Ohio. With the method of full-seam mining that has been adopted, draw slate is shot down, loaded with the coal, and removed in the preparation plants. The roof coal then becomes the permanent roof. The major problem in mining the No. 8 seam in eastern Ohio is control of the roof. Since the strata above the draw slate contains no material with a structure firm enough to provide self-support, the roof begins to sag in a relatively short time after the coal and draw slate have been removed. The problem thus becomes one of getting temporary safety posts under this roof as quickly as possible to prevent a break or separation from occurring either in the roof coal or in the conglomerate above it. Haulage System The Pittsburgh No. 8 seam in eastern Ohio is relatively level, with only minor local dips. Throughout the Hanna Coal Co. mines, entries are generally 12 ft wide. Rooms are driven on a 60" angle on 30-ft centers and are 22 ft wide. No attempt is made to extract the 8-ft pillars between. The entire length of main line haulage is gunited in one mine, and a major portion in another. Two of the mines have single-track main haulage roads with passways. The third, a new mine, is double-tracked, and the roof is supported by steel crossbars, 60 lb or heavier, spaced on 4-ft centers and lagged. In recent years timbering on main line and secondary haulage roads has been accomplished by one of two methods: 1—crossbars are supported on a small section of post set in a hitch hole in the rib, or 2—or a hole is drilled in the rib about 12 in. below the roof, of sufficient depth to fasten securely a short length of 40-lb rail, the bottom of the rail facing the roof, on which a short post is set directly under the crossbar. At present the hitch-hole timbering method is favored. At two of the mines the main line haulage locomotives are 26-ton, 8-wheel units. These locomotives are of the axleless type, each wheel being individually mounted on the frame. The motorman's compartment is encircled by 3-in. armor plate for the protection of the occupants. At the third underground mine conventional 15-ton locomotives are being used. However, these locomotives have been completely rebuilt in the company's shops. Equipment has been streamlined and quarters have been provided for two people, who are protected by heavy steel plate in much the same way described above. This modernization program has been completed on all secondary haulage locomotives at the three mines, and the company is well on the way to similar equipment of the 6-ton section locomotives. The following additional features have been included in their modernization: 1—additional support for the motors to prevent their falling to the middle of the track and derailing the locomotives should a break occur in the suspension bar support; 2—installation of additional bracing to prevent brake rigging from becoming displaced and causing derailments; 3—enclosure of all electric wiring in conduit or raceway; 4—provision of an enclosed compartment for the storage of re-railers, jacks, and other equipment, so that they need not be carried on the outside of the motor; and 5—redesign of the end of the locomotive opposite the operator's compartment to prevent anyone's mounting from that direction. It is interesting to note that some

Jan 1, 1955

By G. B. Misra

While investigating on the aerodynamic resistance of airways supported with peripheral timber sets, at regular intervals, the following theoretical equations were developed by the author to estimate the resistance coefficient of such airways: [ ] for S < 1, where f is Darcy-Weisbach resistance coefficient of the airway, C is modified drag coefficient of the supporting member, D is equivalent diameter of the bare airway, 8 is ratio of the approach velocity over the sets to the average velocity of the bare airway, A is cross-sectional area of the bare airway, a is projected frontal area of the sets, A., is cross-sectional area of the air stream at the vena contracta inside the set, S is spacing of the sets, f, is resistance coefficient of the bare airway, l is length of aerodynamic influence of sets, p is perimeter of the bare airway, p, is setted portion of the perimeter of the bare airway, pe is unsetted portion of the perimeter of the bare airway, and P shielding factor. The equations were verified experimentally in a model rectangular airway supported with one- (bars), three-, and four-piece sets of square-section timber of three different sizes and were found to hold true. The work has been further extended to one-, three-, and four-piece sets of round timber of 2.6, 3.2, and 3.8 cm diam with the same experimental set up. Tests have been carried out for spacings of 25, 50, 75, 100, 150, and 200 cm over a regime of flow defined by the Reynolds number (with respect to the equivalent diameter of the bare duct) ranging from about 1.5 X 106 to 5 X 106 using the same experimental techniques. The values of f are calculated in the manner indicated in [Ref. 1]. Unlike with square-section timber, the resistance coefficient f of the airway setted with round timber shows a distinct variation with the Reynolds number of flow. This conforms to observations made by Sales and Hinsley.2 In order to have a comparable value of f for all types of sets with all sizes of timber, it was necessary to select the value of f at a fixed Reynolds number of flow. Since f is chiefly a function of the drag coefficient of the sets, the appropriate Reynolds number RE is that with respect to the diameter of timber in the set. Considering the diameters of timber used and the regime of flow over which measurements were made, f was chosen at a value of RE = 20,000 in all cases. The f vs. S curves are maximal in nature and in conformity with theory, the f vs. 1/S curves are straight lines up to a value of S = 1 beyond which they show a distinct flexure. The observed values of 1, the length of aerodynamic influence of sets, agree with the relation 1 = 42 e, developed for square-section timber sets, thus suggesting that the shape of timber has little influence on the length of aerodynamic influence. The value of the modified drag coefficient CD for round timber was calculated in the same way as for square timber in Ref. 1, taking the contraction factor Z = 1.5 for round-edged constrictions. CD has an average value of 0.96 with a standard deviation of 6.08% as compared to the free stream drag coefficient of 1.2 at RE = 20,000 for long cylindrical obstructions The shielding factor [ ] is plotted against S/1 in [Fig. 1]. The curves are more or less independent of the size of timber, but are different for the different types of sets, possibly due to their different degree of symmetry. Values of f calculated by the author&apos;s [Eqs. 1 and 2], using experimental values of CD&apos; and [ ] and taking I = 42 e, are plotted in [Fig. 2] against experimentally measured values of f for different types of sets with different sizes of round timber. The values agree closely with a standard deviation of only 5%, thus establishing the veracity of the theoretical equations developed by the author for round timber as well. A comparison was made between the Xenofontowa4 equations (the only other reasonable relations available for the estimation of the resistance coefficient of supported airways) and the author&apos;s [Eqs. 1 and 2] by comparing in [Fig. 3] the values of the resistance coefficient f computed by the Xenofontowa relations with those experimentally measured by the author. In order to make

Jan 1, 1975

By C. S. Barrett, A. Smigelskas

There have been no publications of the deformation and recrystallization orientations of the metal beryllium, yet pronounced textures would certainly be anticipated since it is close-packed hexagonal in structure. Having an axial ratio approximately that of magnesium, beryllium probably deforms by nearly the same slip and twinning mechanisms that operate in magnesium, and the textures are likely to be similar or but slightly different from the magnesium textures. In the tests reported below this is found to be the case; the textures are found to differ from those of magnesium only in the details of the scatter from the average orientation. This report covers not only samples rolled at room temperature, but some rolled at elevated temperatures. Since magnesium has been suspected by some investigators of altering its crystallo-graphic deformation mechanism at elevated temperatures, it was considered possible that beryllium might do so and alter its textures accordingly. No pronounced alterations were found, however. Unfortunately, the theory of deformation textures is not in a state of development that permits one to deduce the deformation mechanism from a knowledge of the textures, which means that the similarity of textures at different rolling temperatures, reported here, cannot be taken as definite evidence that the deformation mechanism is actually the same at all temperatures. The general similarity of the deformation textures of magnesium and beryllium also extend to the recrystallization textures of the two metals, judging by the pole figures for recrystallized sheet presented in this report. Samples were prepared in the form of composite sheets made up of small pieces stacked in a pile. Each piece was trimmed with scissors so that an edge was parallel to the rolling direction, dipped in paraffin, and assembled into the pack by aligning it under the cross hair of a microscope. As the desired orientation was obtained on each piece it was secured in place by touching with a hot wire to melt the paraffin. A stack of ten or fifteen pieces was built up in this way, then trimmed to the shape of a T; the portion to be X rayed was then etched to the shape of a wire about 0.045 in. diam with 6N HCl. This method of shaping the sample is a modification of that used by Bakarian on magnesium.&apos; The absorption of the rays in the sample was so slight that it caused no difficulty in interpreting the films. Exposures were made with a 0.030 in. diam pinhole, using molybdenum radiation (40 kv, 25 ma, Type A film at 5 cm, 2 to 3 hr exposures). With the recrystallized specimens it was found necessary to oscillate the specimen so as to reduce the spottiness of the lines. A range of oscillation of 5" was SUB- cient to produce reasonably satisfactory patterns, though the quality was somewhat inferior to that of the deformation texture patterns, and only two degrees of intensity were read from the arcs on the films. Typical photo-grams for each of the deformation textures and the recrystallization texture are assembled in Fig 1. The pole figures were plotted in the usual way with the intensity of the various portions of the diffraction rings estimated by eye. Seven to nine films were made of each sample and each was carefully read in plotting the pole figures. Typical series included exposures with the beam normal to the rolling direction and at 11, 26, 41, 56 and 71" to the cross direction, plus two exposures with the beam normal to the cross direction, and at 11 and 79" respectively to the rolling direction. The rolling was in each case considered sufficient to develop the final texture: the reduction by cold rolling was 84 pct (from 0.0045 to 0.0007 in. thickness), following prior hot rolling in longitudinal and transverse directions and recrystallization; the reduction by hot rolling at 800°C was 90 pct (0.010 to 0.001 in.), following similar prior treatment; the reduction by rolling at 350°C was 88 pct (from 0.005 to 0.0006 in.) after similar prior treatment. The recrystallization texture was determined on a sample rolled at 350" to a reduction of 88 pct (0.0165 to 0.002 in.) after similar prior treatment, then mounted between steel strips to keep it flat and annealed at 700" in an atmosphere of argon. Discussion of Results The results of the X ray determinations are assembled in the pole figures of Fig 2, 3, 4 and 5 for rolling at

Jan 1, 1950

By K. E. Nelson

The effect of thorium and zinc variations on the strength and 100-hr creep characteristics of Mg-Th-Zn-Zr alloys was investigated. Optimum resistance to creep at 650° and 700°F are attainable within a certain range of thorium and zinc contents. This range does not conform to that which develops maximum tensile properties. RAPID advances have been made during the last few years in the development of magnesium alloys for elevated temperature applications demanding high resistance to creep. The beneficial effect of rare-earth metals on the creep resistance of magnesium alloys has been emphasized by a number of publications1-13 and such alloys are now in commercial production. The use of thorium as an alloying ingredient in magnesium was mentioned by McDonald and also in two Alien Property Custodian patent applications.10,17 The initial observation of Sauerwald that thorium contributes still higher creep resistance to magnesium than is attainable with rare-earth metals has recently been substantiated.&apos;" " In fact, it has been demonstrated that the useful temperature range of magnesium alloys is appreciably extended by the use of thorium. In all cases, it was observed that zirconium must be included in the alloys in order to render them fine grained and more readily castable. Several recent publications:2-27 indicate that a still further improvement in creep resistance and a further extension of the useful temperature range can be realized by the addition of zinc to alloys. The primary purpose of this paper is to present the results of a comprehensive study of the effect of zinc on the strength and creep characteristics of Mg-Th-Zr alloys. Compositions covering the range of thorium content from M to 6 pct and zinc content from 0 to 5 pct have been investigated. The creep characteristics at 650" and 700°F reported in this paper are based on results of tests of 100-hr duration. It is appreciated that creep tests of 100-hr duration might not yield adequate data for design purposes for parts with much longer expected life. However, for the purposes of the present discussion, it is felt that the combination of stresses and temperatures used in the 100-hr creep tests have yielded a clear representation of the compositional variation of creep resistance at the temperatures investigated. Creep tests of 1000-hr duration are now in progress on a few of the most promising alloys. Preparation and Testing of Alloys The alloys studied in this intensive investigation were prepared in 25 lb capacity mild steel crucibles. The thorium, zinc, and zirconium were alloyed and poured as described in earlier publications The thorium was introduced into the melt in the form of a Mg-Th hardener," the zinc added in the metallic form, and the zirconium alloyed in the form of the commercial hardener containing magnesium and 30 to 50 pct Zr.10, 26 Fluxing practices for melting and refining were the same as for magnesium-rare-earth metal-zirconium alloys. The melts were sampled for analytical determinations and poured into separately cast 1/2 in. diameter standard tensile bars. The test bars were given a precipitation treatment of 16 hr at 600°F in laboratory furnaces. It has been shown by other tests that a high temperature solution treatment followed by an aging treatment is unnecessary for the development of optimum properties in Mg-Th-Zn-Zr alloys. The selection of 600°F as the aging temperature was based on an attempt to achieve metallurgical stability without coalescence of the undissolved phases and the attendant loss in strength. The thorium, zinc, and zirconium contents of each melt were determined chemically. The zirconium contents are reported in two parts, "soluble" and "insoluble," referring, respectively, to the portions present in the alloy which are soluble and insoluble in dilute HCl acid. Distinction is being made between these two components of the zirconium content in the alloys because it has been found that only that portion of the zirconium content which is soluble in dilute inorganic acids affects the structure and properties of the alloys. The usual impurities consisting of copper, iron, manganese, and nickel were determined spectroscopically. The analysis for each melt is listed in Table I. A description of the methods of tension and creep testing has been detailed in earlier papers. The tests were performed with the cast skin re-

Jan 1, 1954

By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick&apos;s law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring&apos;s rate theory equation and Sheibel&apos;s correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique&apos; with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961

By T. Watanabe, S. Karashima, H. Oikawa

Creep tests of a! iron and its solid-solution Fe-Mo, Fe-Co, and Fe-Si alloys with bcc structure were conducted under constant stresses in ferromagnetic and paramagnetic temperature regions above 0.5T,(T, is the absolute melting temperature). It was found their high-temperature creep behavior changed in the vicinity of the magnetic transformation temperature, that is Curie temperature, TC. In the ferromagnetic region below the steady-state creep rates were lower than those expected from the extrapolation of the data in the paramagnetic region, the amount of decrease being affected by solute addition. Also, activation energies for steady-state creep were different in the two temperature regions. The observed changes were concluded to be due to the effect of ferromagnetism on diffusion. It is well-known that plastic deformation of metals and alloys in the temperature region where mobility of atoms becomes high enough is controlled by atomic diffusion." Many experimental results394 on fcc and hcp materials have been reported to confirm this view. In bcc metals and alloys, not much basic investigation of creep deformation has been performed. In particular, experimental work on iron5-&apos; and its alloys, covering a quite wide temperature range is extremely scarce. On the other hand, the effect of ferromagnetism on diffusion has recently been demonstrated in a iron and its alloys;&apos; it has been made clear that diffusion rates in ferromagnetic temperatur~e region are significantly lower than those expected from diffusion measurement in the paramagnetic region. Therefore, it is concluded that the magnetic effect influences the high-temperature creep behavior in a! iron and in its alloys. The present authors have conducted creep experiments on a iron and its solid-solution alloys over a very wide temperature range, and have demonstrated the magnetic effect. A part of the result has already been reported elsewhere.26 In this paper, the experimental results will be described in detail. While the manuscript was in preparation, a similar magnetic effect on creep deformation of a iron was reported by Ishida . Though their experiments covered an extremely wide temperature range, the creep stresses varied from several thousand psi to several ten thousand psi with decreasing temperature. Consequently, it may be said that there remain some questions concerning their results. I) EXPERIMENTAL PROCEDURE The materials used in the experiments were pure iron and its alloys; they were prepared by vacuum melting (10"" mm Hg) electrolytic iron (99.9 pct), molybdenum powder (99.9 pct), ultrapure silicon, and cobalt pellet (99.5 pct) in alumina crucibles. The ingots were hot-forged to plates 10 mm thick and 50 mm wide, and then were hot-rolled at about 700°C into sheets 1 mm thick. Creep specimens, 5 mm in width and 15 mm in gage length, were machined from the sheets. They were annealed at temperatures which were well above their respective recrystallization temperatures. The chemical compositions of the metal and alloys are shown in Table I together with their heat treatments. High-temperature creep tests by the use of a lever-type creep testing machine were carried out in argon atmosphere under constant tensile stress. In order to keep &eep stress constant within about *0.5 pct, stress change due to specimen elongation was compensated by tensile force of a stainless-steel bellows which was inserted between the loading lever and lower specimen grip with the assumptions of a linear relationship between change in cross section and strain and uniform strain along the section. Beyond the limit of compensation by the bellows, small amounts of load were removed after appropriate strains. The testing temperatures were maintained to within i2"C of the reported values. Creep deformation was auto-graphically recorded at the upper (moving) specimen grip using a linear differential transformer which was held by a stainless-steel rod mechanically connected to the lower specimen grip. It was also directly measured with a dial-gage reading to -& mm. 11) EXPERIMENTAL RESULTS AND DISCUSSION 1) Creep Curves of a Iron and Its Alloys. Creep curves of a! iron, Fe-Si, Fe-Co, and Fe-Mo (<2 at. pct Mo) alloys usually consisted of three stages, that is transient (primary), steady-state (secondary), and accelerating (tertiary) stages. An example is illustrated in Fig. 1 for a! iron. However, in Fe-Mo alloys with more than 2 at. pct Mo, an inverse transient creepZ8 was observed as indicated in Fig. 2. The inverse behavior, which varied with the amount of molybdenum, may be due to the substructure* in the annealed specimen as was sug-

Jan 1, 1969

By G. A. Swanquist, E. M. Morales

INTRODUCTION The idea of water management and control at the Church Rock Mill operations began to take shape in February 1979. At that time, we were already investigating the feasibility of decreasing the fresh water requirements so that the solids would become the limiting factor in tailings impoundment utilization. The area for solution evaporation could be kept at a fraction of the normal requirements under the standard process of full water usage. The Church Rock Mill is an acid leach circuit followed by solids/liquid separation with thickeners in counter current decantation, and solvent extraction. Following the normal design of acid leach circuits, reuse of tailings solution was not incorporated in the original mill process design. INITIAL WATER CONTROL INVESTIGATIONS The investigations to decrease the fresh water requirements centered around modifying the grinding circuit from the present semi-autogenous grinding (SAG) mill in closed circuit with hydrocyclones, to open circuit grinding with a rod mill. The open circuit grinding with the SAG mill and rod mill in series had the potential of decreasing the water requirements for grinding and leach dilution by approximately 50% or 1.4 m3/min (300 gpm). The grinding pulp density would be maintained at 70 to 72% solids, and the leach dilution to 50% solids would be accomplished with acid tailings liquor recycle. In such a grinding circuit arrangement, the SAG mill would provide the primary or coarse grind, and the rod mill would be used for the fine grind. By the SAG mill and rod mill series grinding method of water control and other secondary water controls in various places downstream from the grinding circuit, the required necessary evaporation area was estimated at 120 acres of liquid surface. A second method of water control at grinding was investigated. A two-stage cyclone classification circuit appeared to have a good potential of achieving the same water reduction at a much lower capital and operating cost. However, in retrospect, this would not have been a viable method since a high slime recycle load would have been established hindering classification. The use of reagents to neutralize the acid tailings solution was not considered seriously at that time, since it would have materially increased operating costs, although it would have also allowed more tailings solution recycle and consequently, less fresh water usage. However, with the tailings solution deposition area available at that time, it was not then necessary to incur the high cost of neutralization. The control expected by the series grinding of semiautogenous and rod mills would have been sufficient to maintain a water consumption/evaporation equilibrium well in line with the available land area. IMPLEMENTATION OF NEUTRALIZATION OPERATIONS During the summer of 1979, the UNC Church Rock Mill experienced a tailings dam breach which resulted in a prolonged mill shutdown. Upon resumption of operations at the end of October 1979, tailings deposition was restricted to a small portion of the tailings impoundment area. Figure 1 shows the general tailings area and the limits of the present deposition area in the central part including the borrow pits. These borrow pits had been excavated to provide materials for tailings dam construction. Immediately after resumption of operations, it became evident that it would be necessary to control the quantity of liquid to be evaporated because of the small confined area available for tailings solution deposition and to maximize the deposition time in the tailings area. The water control required had to be exercised on a large scale, and to be in operation as quickly as possible. An obvious solution was to reuse the tailings liquor in mill process. Immediate steps were taken to install the necessary equipment for tailings neutralization on an interim basis. Anhydrous ammonia was selected as the primary neutralization reagent since it was the quickest system that could be placed in operation. Previous laboratory tests indicated fair results with ammonia neutralization. Such a system required a minimum of installed equipment and handling. INITIAL NEUTRALIZATION OPERATIONS Actual neutralization operations began on November 26, 1979. The raffinate solution which normally would have been discarded was pumped to a 3.7 m (12ft) diam by 4.3 m (14ft) tank for reagent contact, see Figure 2. At this tank, anhydrous ammonia was added directly from the tanker trailers and controlled at pH 7.0 nominally. Agitation was provided by air sparging. The neutralized product formed a highly viscous slurry in the grinding circuit which resulted in pumping and cyclone classification problems.

Jan 1, 1982

By M. Bevis, A. F. Acton, P. C. Rowlands

Defor~nation twinning and transformation twinning modes most likely to be operative in Fe-Ni and Fe-Ni-C martensites have been determined using a new theory of the crystallography of deformation t~inning.~ This analysis shows that potentially important conventional and nonconventional twinning modes1 have been omitted in previous analyses. Discussion is given on the relevance of the predicted twinning modes to the lattice invariant shear associated with the martensite transformation in steels and to anomalous deformation twinning in Fe-Ni-C martensites. THE two most important criteria which appear to govern operative twinning modes in metallic structures1 are that the magnitude of the twinning shear should be small and that the twinning shear should restore the lattice or a multiple lattice in a twin orientation. The latter criterion ensures that the shuffle mechanism required to restore the structure in a twin orientation is simple. These criteria have been adhered to in the prediction of twinning modes2"6 in bcc and bct single-lattice structures with axial ratios in the range y = 1 to 1.09 as, for example, encountered in martensite occurring in steels. Refs. 2 and 3 in particular consider the martensite transformation in steels and the twinning modes in these cases relate to transformation twinning, and hence the lattice invariant shear associated with the martensite transformation. The list of twinning modes which can be compiled from these sources is incomplete and the ranges of magnitude of shear considered could be unrealistically small, particularly in the case of deformation twinning. The latter consideration is supported by the fact that twinning modes with magnitudes of shear large compared with the smallest shear consistent with a simple shuffle mechanism have been established in, for example, the single-lattice structure mercury7 and the multiple-lattice structure zirconium.&apos; In addition the anomalous deformation twins reported by Ftichrnan4 to occur in a range of Fe-Ni-C martensites still remain unexplained. It is clear that a comprehensive analysis of twinning modes likely to be operative in martensite In steels is required. The results of the application of a new theory of the crystallography of deformation twinningg to these structures are presented in this paper. The theory has been used to determine all shears which restore the lattice or a multiple lattice in a new orientation with magnitude of shear up to a required maximum. The orientation relationships between parent and twinned lattices are not restricted to the classical orientation relationships of reflection in the twin plane or a rotation of 180 deg about the shear direction. PREDICTED TWINNING MODES Twinning modes which restore all or one half of lattice points to their correct twin positions will be referred to as m = 1 and m = 2 modes, respectively. These modes are the most likely to describe operative modes in single lattice structures. The bcc m = 1 and m = 2 modes which have magnitudes of shear s in the range s < 2 and s < 1, respectively, have been given10 and are reproduced here in Tables I and 11. Detailed discussion of the crystallography of these modes and cubic modes in general will be discussed elsewhere (~evis and rocker, to be published). The four twinning elements Kl, &,ql,7)2 as well as the magnitude of shear s are given for each twinning mode, and the twinning modes are given in order of increasing shear. Two twinning modes are given in each row of the tables, the twinning mode Kl, Kz, ql, q2 and the reciprocal twinning mode with elements Kl = K,, Ki = Kl, q: = q2, and 17; = ql. The m = 1 and m = 2 twinning modes which describe twinning shears with small magnitudes of shear and simple shuffle mechanisms in bct crystals with -y = 1 to 1.09 are given in Tables I11 and IV, respectively. On increasing the symmetry of the tetragonal lattice to cubic, that is making y = 1, all modes listed in Tables 111 and IV must reduce to crystallographically equivalent variants of the modes given in Tables I and 11, respectively, or become twinning modes with both shear planes as symmetry planes in the cubic lattice and hence not considered in Tables I and 11. With the exception of this last type of mode only those tetragonal twinning modes which reduce to modes 1.1, 1.2, 2.1, and 2.2 of Tables I and I1 are considered in Tables 111 and IV. For values of y in the range -y = 1 to 1.09 the tetragonal modes and the corresponding cubic twinning modes have approximately the same magnitude of shear. The twinning modes listed in Tables 111 and IV are therefore by the criteria given above the most

Jan 1, 1969

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800&apos; and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,&apos;,&apos; in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of &apos;nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;&apos; this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.&apos; characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,&apos; have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)&apos; and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn&apos; through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By Roland J. Lapee

A history of the progress made in copper refining in Montana is presented. The casting furnaces and the newly rebuilt electrolytic refinery are descmbed and operating details are given. Experiences with various addition agents, effects of rernoval of chlorine from the electrolyte, and effects of separan on electrolyte and on copper deposit are discussed. Observatzons are made on the effect of various impurities in anode copper and behavior of thezr salts in electrolyte and in slime, on treatment of slime for removal of copper, and on electrolyte puriification problems. The improved method for production of starting sheets is described. Attention is given to new materials for construction and to improvement in matrials handling ad quality control. COPPER refining at Great Falls, Montana, dates back to 1892. The original plant produced 65,000 lb. of cathodes per day at a current density of 16 amp per sq ft. In this plant anodes and cathodes were handled to and from the cells by means of hand-operated chain blocks and were moved about the plant by hand trucks. Cathodes were melted in coal-fired, reverbera-tory furnaces, were charged by hand, and refined copper was dipped by hand and cast in iron molds. In 1916, a new, modern plant with capacity to refine 18 million Ib. copper per month was built. Two refining furnaces were built, and each was provided with a twenty-mold Clark casting wheel. In 1922, the furnaces were converted to the use of pulverized coal: in 1923, to the use of oil; and in 1928, to the use of natural gas. In 1926, the plant was enlarged 50 pct. The use of pulverized coal for refining copper at Great Falls was discussed1 in a paper presented at the Salt Lake City meeting of the Institute in September 1925. Also, a comparison of the use of various fuels in copper refining furnaces was discussed 2 in a paper presented at the New York meeting of the Institute in February 1932. Prior to 1943 the cellroom was operated with twenty-five 720-lb. anodes and 26 cathodes per cell. Four cathodes, each weighing about 165 lb., were produced from an anode. In 1943 the weight of the anode was reduced to 460 lb., and two cathodes, each weighing about 190 lb., were produced from an anode. In 1949, a Billet Casting Wheel for the production of 3 in. diam phosphor deoxidized billets was built. A paper, presented at the New York Meeting of the Institute in February 1956, describes3 this plant and operation. In the electrolytic refinery, production is controlled by variation of the current density. In 1956, germanium rectifiers on a separate electrical circuit were provided for the starting sheet section so that current density could be maintained at any desired figure. Also in 1956, a program of modernization and enlargement of the Electrolytic Copper Refinery was started. This program, when completed, will raise the capacity of the Great Falls Electrolytic Copper Refinery approximately 33 pct, to 33 million lb. of cathodes per month. Furnace capacity for melting cathodes and anode scrap is ample to take care of the increased production from the electrolytic refinery. This fortunate condition came about primarily as the result of the three following changes: 1) The furnaces were lengthened 10 ft in 1922 when the fireboxes were found unnecessary for burning powdered coal. 2) Furnace life, and hence furnace capacity, was increased by the successful efforts of the Copper Refinery staff to develop a method for sanding furnace side walls and roof. 3) The natural gas being used has a very low sulfur content. As a result, it is possible to reduce time spent rabbling and poling and thus greatly increase tons per furnace charge. TANKHOUSE AND TANKS The Great Falls Electrolytic Refinery is 535 ft long by 252 ft wide. The cells are arranged in four crane bays in which are operated seven 10 ton Whiting Cranes. The old cells are in groups of ten, with circulation of electrolyte through five cells in cascade and with aisles between the groups of ten cells. The new cells are nested in groups of sixteen with no aisles, are all on one level, and have individual circulation to each cell. Present plans call for 1792 commercial cells and 128 stripper cells. To reduce confusion during the construction period, and to use the cranes, cars, and other equipment already on hand, the cells in the rebuilt section were designed to have approximately the same inside dimensions as the cells in the old part of the

Jan 1, 1962

By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K&apos; = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950

By M. H. Yoo

Possible interactions of the perfect dislocations of six slip systems or the c dislocation with the (10i2f (ioii), {ioIi}(ioiZ), {1122}(1123), and {1121}(ii26) type twins in hcp metals have been analyzed from the crystallographic and the energetic points of view. Twenty-six distinct types of possible interactions were identified, and those selected based on crystallographic constraints were examined for their energetic feasibilities by use of the anisotropic energy factors. No long-range elastic interaction exists for a dislocation when its Burgers vector is parallel to the twin interface. Under a suitable applied stress, a screw dislocation can cross slip at the twin interface. For basal mixed dislocations in cadmium and zinc, the interaction with {1012} twins is found to be attractive, indicating that incorporation of these dislocations into the twins is energetically feasible and that twin growth will result. On the other hand, the interaction between both basal and Prism mixed dislocations and the {1012} and (1121) twins is found to be repulsive in Mg, Co, Re, Zr, Ti, Hf, and Be. This indicates that under an applied stress a local stress concentration will develop due to a dislocation pileup at the interface, which may result in a site for either the nucleation of other twins or the formation of a crack, depending on the cleavage strength. WHEN a metal undergoes plastic deformation, a certain configuration of slip dislocations will result in a state of dislocation pileup against an obstacle. The stress concentration thus developed may enhance the process of twin nucleation and also twin growth. Furthermore, once formed and dispersed in the crystal, twins can act as effective barriers against slip dislocations. The degree of such mutual influence or interrelation between slip and twinning is generally known to be pronounced in the case of hcp, metals. It is also known that deformation by twinning occurs more commonly in hexagonal metals than in cubic metals. In fact, under suitable stress states, all hexagonal metals exhibit {1012) <1011> type twinning.&apos; In addition to this common type, deformation by (1151) <1126> type twinning occurs in zirconium, titanium, and rhenium, which show remarkable ductility.&apos; The importance of twinning during general deformation to the ductility of hcp polycrystals has been briefly discussed in recent review works.2&apos;3 The purpose of this paper is to analyze the interaction between slip dislocations and twins in the hcp structure and to discuss the nucleation and growth processes of twinning and the role of twinning in the <"°" noil) o, 1/3[112O] (OOO2) 1/3[1123] Fig. l—-Slip systems in hcp structure. ductility of hexagonal metals. The problem will be discussed from the geometric and the energetic points of view in a manner similar to that of the previous work on zinc.4 Since hcp crystals deform by several slip and twin systems, numerous interactions result as possibilities. The Burgers vectors of six slip systems and the c dislocation shown in Fig. 1 and the four twin systems listed in Table I are considered here. A complete tabulation of the possible interactions is followed by discussion of those that are more likely to occur on the basis of crystallographic constraints and energetic considerations. 1) CRYSTALLOGRAPHY OF TWINNING The crystallographic elements, K1, K2, n1, and n2, for the four compound twin systems are now well established.= A unit cell with the base vectors n1, and n2 is shown in Fig. 2 for each twin system. The unit cell before twinning is shown in solid line, and the corresponding unit cell after twinning is shown in dashed line. Also shown in Fig. 2 are the following crystallographic parameters: S is the plane of shear, d the interspacing of the twin habit planes K1,Ø Iis the acute angle between n1, and n 2, e is a numerical factor, and q is the number of K, lattice planes intersected by 17&apos;. These parameters can be expressed in terms of the axial ratio, y = c/a, as listed in Table 11. The macroscopic shear strain of twinning, s, and the magnitude of a "unit twin dis-l~cation,"4 bt, are also expressed in terms of y and given in Table 11. In Table 11, K1 and q1 are given in both Miller-Bravais and Miller indices. In double lattice structures, shuffling of atoms in addition to a homogeneous shear of the lattice is generally required if the original crystal structure is to be restored after twinning. The extent of current understanding on this problem of atom shuffling is per- Table I. Four Twin Systems in Hcp Structure

Jan 1, 1970

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

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

Jan 1, 1960

By W. A. Tiller, W. C. Johnston

A high-temperature electromagnetic stirrer is described in which heating and stirring are accomplished by independently controlled power sources. The appavatus is suitable lor use at temperatures up to 1700°C in a variety of ambient atmospheres. Some typical examples of the homogenizatimz capabilities of the system are given. THERE are few processes in solidification that are not markedly affected by motion in the melt during freezing. In many instances, the mechanisms are diffusion-controlled, and the transport in the melt may be greatly accelerated by deliberately stirring the melt. In zone-refining, stirring1 assists the removal of rejected impurities from the interface, so the process proceeds at a faster rate. The transition from a planar to a cellular interface is caused by constitutional undercooling in the melt ahead of the interface: and stirring delays its onset. Stirring is valuable for homogenization of melts: and chemical reaction with sluggish kinetics may be accelerated. Finally, it has been observed that grain refinement is related to motion in the melt. Fine grain castings are usually produced by the addition of catalysts to the -melt,&apos; catalysts which are thought to act simply as hetereogeneous nucleation centers. Even here motion is important. Richards and Rostoker 5 applied ultrasonic vibration to a solidifying A1-Cu alloy which had been innoculated with a catalyst and found that the grain diameter fell linearly with the amplitude, the peak acceleration and the power input to the melt from the transducer. Finally, mechanical and electrical stirring alone have been used to generate a fine-grained structure.6,7 Johnston ef a1.&apos; have carried out a series of systematic investigations of grain refinement by electromagnetic stirring in a number of low melting point alloys. They found, for example, that the number of grains per unit volume in Pb-Sn alloys could be increased several orders of magnitude by stirring an undercooled melt at the moment of recalescence. In general, a relation AT .H = constant prevailed for a given grain size, where AT was the undercooling of the melt and H the field strength. In more recent work, deliberate homogeneous nucleation of slightly undercooled melts established that the mechanism of refinement must be one involving crystal fragmentation and subsequent multiplication, rather than a "shower" of nuclei effect.9 It is the purpose of this note to describe a stirring device suitable for use up to 1700°C. At low temperatures mechanical stirring and direct-current methods are feasible, but at high temperatures the problem of a protective atmosphere and of electrode corrosion rules out such procedures. The most convenient method for high temperatures is to use externally generated ac fields for both stirring and heating. With rf induction heating alone, considerable stirring and agitation can be achieved, but in general the penetration of field into the melt is small, and the stirring cannot be controlled independently of the heating. In the present experiments, separate power sources of different frequencies for heating and for stirring were used. A susceptor design was chosen so that the 450 kc rf heating field was completely absorbed in the susceptor. The stirring frequency, 400 cps, hereafter called the af field, was chosen so that a high penetration of the melt proper was achieved. EXPERIMENTAL APPARATUS The apparatus, Fig. 1, consists of a quartz tube and end plates, surrounded by an rf induction coil and six equally spaced af stirring coils, four of which are shown in full and a fifth in section. Each af stirring coil is a transformer of which the secondary is a single-turn water-cooled copper loop and the primary is composed of two 10 amp-117 v Variac cores as shown. These cores are cooled by forced air, as each of the six pairs will carry maximum currents of 15 amp for short periods. Each set of Variac windings are connected in series, but opposite sets are connected in parallel with a three-phase 400 cps 400-v source. By properly phasing the coils in this way, a rotating field is produced. Capacitors C1, C2, and C3 in Fig. 2 are used to match this inductive load to the generator. Fig. 3 shows a cutaway view of the quartz tube. The sample (1 in. diam by 1 in. high) is placed in a tapered alumina crucible. An axial W-26 pct Re thermocouple, enclosed by a protection tube, is provided. The cruci-

Jan 1, 1968

By B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable &apos; any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By D. S. Tomalin, D. F. Stein

The effect of reducing oxygen to low concentrations on the fracture of high-purity iron single crystals has been examined at 78° and 20°K. It is found that iron single crystals grown by the strain-anneal method usually contain a few occluded grain boundaries which may become embittled in the presence of oxygen, thereby nucleating cleavage fractures. High purity with respect to interstitial elements was found to inhibit twinning and evidence is presented for an orientation dependence of the resolved yield stress. Deformation occurred by slip rather than twinning at both temperatures of testing with elongations of as much as 9 pct at 20°K. THE fracture properties of iron single crystals have been observedl-3 to be a function of temperature, orientation, and purity. Allen, Hopkins, and McLennan1 demonstrated that at 78°K iron single crystals became increasingly brittle as the tensile axis approached the (001) pole of the stereographic unit triangle. Iron crystals with the tension axis near a (001) pole were completely brittle and orientations near the (011)-(111) boundary were very ductile, achieving a 100 pct reduction in area prior to fracture. Later work of Biggs and pratt2 and of Edmondson3 demonstrated that by reducing the carbon content of the single crystals the transition between brittle and ductile failure at 78°K could be shifted to orientations nearer the (001) pole. Ed-mondson went further and pointed out that any mechanism which tended to increase the yield strength of the iron (i.e., carbon addition, pre-strain) also increased the tendency for brittle behavior at 78°K. Thus by a reduction of carbon content Biggs and Pratt were able to obtain ductile behavior to within 20 deg of the (001) pole, and Ed-mondson was able to obtain ductile behavior to within 26 deg of the (001) pole. Edmondson&apos;s material had a total interstitial content (carbon, oxygen, and nitrogen) of approximately 60 ppm and, although Biggs and Pratt reported no analysis, indications were that their iron contained comparable impurities. Stein, Low, and seybolt4 purified iron single crystals to a total carbon, oxygen, and nitrogen content of approximately 20 ppm. They observed a lowering of the yield stress with this increased purity, and thus one might have expected an observation of increased ductility. Although they tested specimens of orientations which the previous workers had indicated should be ductile, the crystals failed at a 78°K in a brittle manner with little elongation. Stein noted,&apos; however, that about 90 pet of the failures could be traced in origin to occluded grains. Allen et al.1 and Edmondson3 do not report examination of their cleavage surfaces, but Biggs and pratt2 reported that microscopic examination of the cleavage surfaces of many of their specimens revealed the presence of small occluded grains. Honda and cohen6 and Keh7 have also observed the initiation of fracture at occluded grains in iron single crystals. Therefore, the additional complication of occluded grains must be considered in studying the properties of iron single crystals and the origin of fractures determined if the ductility exhibited by the crystals is to be considered meaningful. Various investigators8-12 have studied the effects of impurities on grain boundaries in high-purity polycrystalline iron. Rees and Hopkins10 showed that the addition of oxygen to low-carbon (0.002 pet) iron weakened the grain boundaries, causing a shift from transcrystalline to intercrystalline fracture and a progressive decrease on the brittle-fracture stress with increasing oxygen content. In addition, it has been shown by Low and Feustel11 that the addition of carbon to polycrystalline iron containing oxygen eliminated grain boundary brittleness. Thus, oxygen can embrittle grain boundaries in high-purity polycrystalline iron, but the addition of an appropriate amount of carbon can eliminate the oxygen-induced brittleness. The oxygen content (19 ppm) of the iron "single crystals" employed by Stein el al. was large enough to suspect impurity effects at the occluded grain boundaries. Allen et al.1 Biggs and pratt,2 and Edmondson3 may have masked any occluded grain problem in their specimens considering the relatively high carbon levels they employed. stein13 demonstrated that the addition of as little as 0.9 ppm C to previously purified (less than 5 x 10-3 ppm C) "single crystals" would increase the elongation from a few percent to more than 20 pet at 78°K and the fracture was not associated with grade boundary initiation.

Jan 1, 1965