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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' = [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 F. M. Morris

A large reserve of thick coal in southwest Virginia was developed by Clinch-field Coal Co. in 1957-1958 to produce a nominal rate of 1500 tph raw coal. Operation features coal cleaning in transit. Refuse removed averages 35 pct. Evolution of plant from initial conception to completion is discussed, selection of means applied is explained, and performance to date us design expectation is described. The long-range plan calls for ultimate handling capacity of 40,000 tpd raw coal with anticipated clean coal capacity of 26,000 tpd on a three-shift basis. From a materials handling viewpoint, the Moss No. 3 operation is principally of interest as an ensemble. Generally speaking, it uses time-tested equipment and ideas but some of these are employed on a scale that may be new in the industry. At present about 20,000 tpd of raw coal are being handled. This is expected to increase to 40,000 tpd as soon as business conditions justify it. The purpose of this paper is to discuss the evolution of the plant as to materials handling practices, to describe briefly the equipment and methods used, and to comment on performance in certain areas. The subject divides itself naturally into four phases: 1) operations at the mines, 2) transportation from mines to plant, 3) raw coal handling into the plant, and 4) transportation of refuse away from the plant. OPERATIONS AT THE MINES The coal reserves for Moss 3 are in southwest Virginia where Dickenson, Russell, and Buchanan Counties come together. This area contains about 15 square miles and over 100,000,000 tons of coal. Here the No. 4 (Tiller) and No. 5 (Jawbone) seams of the Norton Formation lie so closely together that for practical purposes, they constitute one seam of coal. This seam, which is called the Thick Tiller, varies from 10 to 18 ft in thickness and underlies Sandy Ridge, a mountain cresting between 2400 and 3300 ft above sea-level. At 18-ft seam height (which is considered to be the maximum practical mining height) the parting between seams will be about 3 1/2 ft thick and each bench of coal will be about 7 ft thick. Depending on the amount of impurities in the seams Drover. total reject in this height coal may approximate 50 pet by wt. It will average about 35 pet for the property as a whole. The first move in developing this resource was made in 1953 when contour maps of several square miles around Duty, Va., including all the known outcrop, were made by photogrammetry. At this time, it was felt the prospective operation would be served by the Clinchfield Railroad and a photogrammetric route survey was made by this railroad from Haysi to Duty. Study of the resulting maps indicated only one site—adversely owned—which might accommodate the size washing plant to be erected. Water resources of a dependable nature seemed nonexistent. In 1954 bulk washability tests were made on the Tiller Bench at the Moss No. 1 preparation plant. The tests indicated this portion of the seam, mined separately, would wash to 4 pet ash with good recovery. Also in 1954, development of Moss No. 2, south of Sandy Ridge, was begun. This mine is in the Tiller Seam where it is about 100 ft below the Jawbone Seam. The reasons for developing a mine in the normal Tiller Seam before tackling the Thick Tiller seemed compelling: Railroad service could be established quickly, communications were better (though not good!), more was known of the seam (it had been mined in the years 1911 to 19241, and there was no essential property to be acquired. After some legal skirmishing, the Norfolk & Western Railroad was granted the right to serve the new mine. Three decades earlier the old mine had been served by the Clinchfield Railroad. The event which triggered active development of Moss 3 was the Appalachian Power Co.'s decision in 1956 to build a 450,000-kva power plant on Clinch River at Carbo. This solved the problem of marketing the steam coal which inevitably must be a product of a mine in the Thick Tiller. Management promptly decided to build the preparation plant at Carbo where an excellent site was owned; where railroad service existed; where telephone service could be obtained; and where roads, bridges, and water supply were tolerable.

Jan 1, 1961

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 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.' 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 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 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 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

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson&apos; obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock&apos; used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

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 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 Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier&apos;s specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.&apos; The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By C. P. Sandberg

Notwithstanding the growing importance of this subject, no work specially devoted to it has hitherto been published. Having had to inspect during the last twenty years nearly a million tons of iron and steel rails for various countries, I have obtained experience of what rail manufacturers can practically execute, as well as of what railway engineers practically require. Bearing these two points in mind, I have from time to time published observations with a view to unite both interests,—that of the producer and that of the consumer,—and to reduce the specifications and the forms of sections to standards, or types, in order to facilitate the execution of the works and to improve the construction of permanent way. The Swedish government railways, as well as private companies owning railways in Sweden, Norway, and Denmark,.have during the time above mentioned consulted with me and intrusted to me their rail inspection. I therefore owe to these countries much of the opportunity which I have enjoyed of gaining experience and position. Next to Sweden, America is the country which has most liberally favored me with its confidence in placing these matters in my hands. Through circumstances not under my control there has been little exportation to, and less work done by Europe for, America during the last six years; but the recent revival of the rail trade has been the more gratifying to mo, seeing that almost all the importers of American rails are still specifying for the Sandberg rail sections and inspection. It is therefore with feelings of gratitude that I now beg to lay before the American Institute of Mining Engineers, and I hope, through that body, before the American railway world, the results of some experience which I have gained in the execution of work for their country, and which therefore belongs rightfully to

Jan 1, 1881

By C. P. Sandberg

INTRODUCTION. NOTWITHSTANDING the growing importance of this subject, no work specially devoted to it has hitherto been published. Having had to inspect during the last twenty years nearly a million tons of iron and steel rails for various countries, I have obtained experience of what rail manufacturers can practically execute, as well as of what railway engineers practically require. Bearing these two points in mind, I have from time to time published observations with a view to unite both interests, -that of the producer and that of the consumer,-and to reduce the specifications and the forms of sections to standards, or types, in order to facilitate the execution of the works and to improve the construction of permanent way. The Swedish government railways, as well as private companies owning railways in Sweden, Norway, and Denmark, have during the time above mentioned consulted with me and intrusted to me their rail inspection. I therefore owe to these countries much of the opportunity which I have enjoyed of gaining experience and position. Next to Sweden, America is the country which has most liberally favored me with its confidence in placing these matters in my hands. Through circumstances not under my control there has been little exportation to, and less work done by Europe for, America during the last six years ; but the recent revival of the rail trade has been the more gratifying to me, seeing that almost all the importers of American rails are still specifying for the Sandberg rail sections and inspection. It is therefore with .feelings of gratitude that I now beg to lay before the American Institute of Mining Engineers, and I hope, through that body, before the American railway world, the results of some experience which I have gained in the execution of work for their country, and which therefore belongs rightfully to

Jan 1, 1881

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 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 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 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 Eduardo J. Chibas

Location.—The principal manganese-deposits of the Department of Panama, Republic of Colombia, are located almost clue south of Viento Frio, a native village bordering on the Caribbean Sea, and about 45 miles northeast of Colon (Aspinwall). The mining-claims are the Viento Frio, the Carrano, the Nispero, and the Soledad. Each property is to the south of the preceding one in the order mentioned. The first one is about one mile from the coast, and the most southerly boundary of the Soledad is about five miles in a straight line from the same coast-line. I shall confine my remarks to the four properties mentioned and to La Guaca, west of the Carrano, because these are the only ones where mining has so far been done to more or less extent. Manganese has also been found, however, in the neighborhood of these deposits, and a large area adjoining them has been divided into sections and " denounced " as mining-claims. The relative position of the manganese-deposits and Nombre de Dios, the present terminal of the railroad and shipping-port, as well as Viento Frio and the adjacent coast, can

Jan 1, 1898