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By W. Hume-Rothery

IN recent interesting papers,1,2 Bardos et al. have described ternary Laves phases of the type A2(BsSi) and A4(B5Si3) where A = titanium vanadium, niobium, and so forth, and B = manganese, iron, cobalt, or nickel; other more complex formulae have also been established. In these phases, silicon plays the part of the smaller B atom of a Laves phase AB2, and the interatomic distances show that the effec- tive silicon radii lie between 1.16 and 1.21Å, and are thus very much smaller than the metallic radius of silicon for CN = 12. It does not seem to have been pointed out that these small atomic radii are almost the sape as the normal covalent radius of silicon (1.174Å). If, therefore, silicon acts as an acceptor of electrons as suggested by Bardos et al.,1 it appears to do so, not by the building up of a negatively charged silicon ion which would be large, but by the formation of what are very nearly or may be actually normal covalent bonds. Since a covalent bond contains two electrons, its formation would reduce the number of electrons available for bonding in other parts of the structure, and in this way the effect of silicon in stabilizing the o phase at high electron concentrations might be understood.

Jan 1, 1965

By R. C. Hall

We are pleased to confirm some of the mechanical data presented by Dr. Detert on the 18 pct Ni marag-ing steel.15 Bar 3 in. in diam and containing 0.02 wt pct C, 18.5 Ni, 8.9 Co, 5.1 MO, 0.55 Ti, 0.05 Al, and balance iron has been examined in our laboratory. Cylinders 0.5 in. high and 0.4 to 0.5 in. in diam were cold-compressed from 3 to 40 pct reduction in height. Table VI shows some typical data; deformation in-

Jan 1, 1968

THE Johnson award for 1926 was given to T. L. Joseph for his experimental work on blast-furnace operation. When the Bureau of Mines undertook its experimental blast-furnace investigation in 1919, a number of operators and metallurgists were doubtful as to the practicability of small-scale tests. Several pre-vious attempts, outside the Bureau, to operate small furnaces had been unsuccessful. However, pig iron was produced in three and four-ton furnaces during the first half of the nineteenth century. The operation of a small furnace did not therefore seem an impossible task. This point of view, together with a realization of the importance of problems connected with the pro-duction of pig iron, prompted the Bureau to undertake this work. Such problems as the feasibility of using charcoal briquets as a fuel, the application of oxygen enriched blast, and the use of new ores and raw ma-terials, in general, can be investigated only at consider-able cost on full sized furnaces, while with an experimental furnace they can be conducted at a com-paratively ;small, cost. The results of small-scale tests are sufficient to determine whether the problem. War-rants the expenditure required for a trial on a com-mercial scale. The accompanying photographs and chart show the various stages of the experimental furnace development. Some idea of the size and shape of furnaces which were tested can be had from the development chart. In oper-ating furnaces A to F, a series of changes were made to increase hearth temperature. Perhaps the most im-portant change was the position of the tuyeres with respect to the bottom of the hearth. The height of the tuyeres above the hearth was gradually increased and the hearth diameter decreased. It was shown by this series of furnaces that metal and slag are the chief source of heat supply to the crucible. For this reason there is a minimum rate at which these materials can be brought into the hearth of a small furnace if it is to function properly. The rate of slag "and metal fall are determined by the burden on the furnace and the rate of blowing. Due to lack of funds necessary to provide ample blowing equipment, hot blast stoves, essential mechani-cal features, and to meet operating expenses, it. was necessary to work with much smaller furnaces, such as G to K shown in the chart. The particular object of these tests was to study the extent to which reactions could be speeded up by decreasing the size of the stock. One decided change, noticed at the beginning of this series of tests, was the effect which coke size had on the production of a strongly reducing gas. Furnace G, 22 in. high, operating on coke crushed to pass 10 mesh, made a gas richer in carbon monoxide than did fur-naces A to F, operating on run-of-the-oven coke.

Jan 3, 1927

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By J. C. Yannopoulos, N. J. Themelis

Ah electronic thermogravirnetric balance was used to measure the veductioiz rule o single cirpric oxide particles suspended in a stream of hydrogen. Very jzne thermocouples embedded in lie center and at the surface of the sphere recorded the variation of terw perature during reduction. In contrast to iron oxide reduction, where in most instances the rate of interface reactiokl is controlling, the heat- and mass-transfer phenotnena play a predolrinant role in the reduction of cupric oxide. The correlation of experitnental data or tnass lransfev lhrough the boundary layer at Reynolds nunlber 0-4 50 was as jollocs: ThE reduction of cupric oxide by hydrogen is represented by the equation: It is a highly exothermic reaction and the amount of heat released varies only slightly with temperature (-21,430 cal per g-mole at 400°C). Most of the published studies on this system have been conducted at temperatures in the range of 34 to 280c.l-&apos; The concensus of opinion has been that at temperatures below 200°C the reaction is preceded by an induction period during which there is very little or no reduction. The length of this period diminishes as the temperature of the reaction is increased1l5 and aseawa found that at 280°C reduction starts practically immediately when the oxide is exposed to hydrogen gas. The existence of an induction, or incubation, period has led experimenters to believe that the reduction of CuO by hydrogen is catalyzed by metallic copper.&apos; Boldurev and rmolaev found that mechanical additions of powdered copper to oxide did not affect its reduction, although metallic copper produced during the reduction seemed to have a catalytic effect. At least three other authors2&apos;5&apos;7 have reported that addition of copper had no effect on the rate of reduction. Pease and alor&apos; observed that water vapor had a strong inhibiting effect on the reduction at 1503C, but its effect was greatly diminished at 200 C. Pavlychenko and Rubinchik5 studied this reaction at 159 to 235 C and found that, once the reaction had been initiated, there was no inhibiting effect due to the introduction of water in the hydrogen stream; at temperatures above 183°C there was no inhibiting effect due to water vapor, either before or during reaction. The same authors noted that the rate of reduction was independent of pressure in the range of 200 to 700 mm Hg. aseawa investigated the kinetics of the CuO-Hz system at 160 to 280°C and estimated the apparent activation energy at 14,000 cal per g-mole. A similar value (13,500 1200 cal per g-mole) was reported by ond&apos; in the temperature range 148 to 216°C. Bond also reported that there was no incubation period and that water vapor had no inhibiting effect on reduction at temperatures above 190 C. The above studies have been conducted at temperatures below 280°C and the physical configuration of the system under investigation has not been defined adequately. However, it is well-known that the mechanism of gas-solid reactions depends on a number of in series physical and chemical rate prcesses.&apos;&apos; It is, therefore, essential to include among the experimental factors the geometry of the solid system and the mass-transport characteristics of the reducing gas. Scott studied the reduction of packed beds of cupric oxide cylinders by Hz-He streams of very low hydrogen concentrations at temperatures 400 to 600 C, pressure of 10 to 30 atm, and gas velocity from 0.18 to 5.8 ft per sec (3 < Rep < 30). The reduction rate was found to be mainly controlled by diffusion through the boundary layer and through the pores of the reduced copper phase. The following correlation was proposed: Scott in an earlier work studied the reduction of fixed beds of cupric oxide wire and found that the rate of flow of the gas stream through the bed had a controlling effect on the rate of reduction. The same mass-transfer phenomenon was observed by Bond and clark13 on a similar reduction system. The analogy between mass and heat transfer through the boundary layer which exists between a solid surface and the bulk stream stems from the similarity of the differential equations representing these phenomena

Jan 1, 1967

By John Stewart

The market at present supplied by shipments from the phosphate districts of Quebec, Ontario, and New York State requires high-grade ore, carrying from 75 per cent. to 90 per cent. of phosphate of lime. In sorting out such material by hand, much valuable phosphate is necessarily left in the "culls" or refuse, besides which, much phosphate-rock of low-grade is not now mined at all, because it cannot be made available by the crude method of cobbing and hand-sorting. The utilization of such material, which would, of course, greatly benefit this industry, requires either a mechanical separation or a chemical process which would concentrate the phosphate in a form suitable for agriculture. Considering the rich phosphate now shipped as the first class, we may arrange the lower grades in three classes, as follows: Second Class.—Cull-ore from the first class, and the mass of deposits having, as gangue, pyroxene or hornblende. The following table gives the hardness and specific gravity of the minerals concerned: Hardness Spec. gravity. Apatite,....... . 5 3.1 to 3.25 Crystalline limestone (pink calcite),. 3 to 4 2.5 to 2.9 Pyroxene,..5 to 6 3.23 to 3.5 Hornblende,.5 to 6 2.9 to 3.4 Feldspar (orthoclase),. .. . 6 to 6.5 2.5 to 2.6 It is evident that when pyroxene and hornblende are present in large proportions, this ore cannot be successfully concentrated by crushing and jigging. It may be reduced to fine powder by successive treatment in a rock-breaker and a Sturtevant or Frisbee-Lucop mill, or other suitable apparatus, and in this condition it could be largely used by applying it freely upon exhausted clay soils, such as occur in Quebec and Ontario. The occupants of these once fertile river-lands are, however, hard to move in the direction of such improvements. When water-power is at hand, the cost of crushing

Jan 1, 1893

By P. Duwez, C. B. Jordan

A. J. SHALER*—I should like to congratulate the authors for having carried out such a precise set of experiments. It has been found useful, in sintering experimental compacts in vacuo, to make certain that the residual gas is not one which reacts with the metal. Since traces of oxygen can be kept away only with great difficulty, the technique is often adopted of using a "getter " of powder in the vicinity of the compacts, and, in addition, of permitting a small hydrogen leak to flow into the vacuum chamber. Did the authors use similar devices? This paper brings up a question concerning the definition of the word &apos; sintering.&apos; The authors restrict its use to the adhesion between particles. Kuczynski, in a paper presented at this meeting, applies the word to the growth of areas of contact between particles. I have used it to mean both these phenomena and also the dimensional changes which continue to take place after the first two have run their course. May I suggest that we should come to an agreement on the use of these words ? Fig 1 and 2 show an interesting feature: extrapolation of the curves to zero time does not give a densification parameter of zero. The higher the temperature, the higher is the intercept on that axis. These observations agree with the concept of a practically instantaneous densification taking place while the compact is being brought to heat. Such a change may be brought about by plastic deformation and primary creep. The stress pattern causing this first rapid flow is, to my mind, due to the force of attraction between the surfaces of opposite particles in the regions immediately flanking their common areas of contact. The stress is not temperature-sensitive, but at room temperature plastic deformation only proceeds until the metal in the area of contact can support it elastically. As the metal is heated, the elastic limit falls, and further plastic flow occurs. At the higher temperatures, this is followed by primary creep, and finally by the steady-state rate-reaction which the authors are seeking. If they were to recalculate their densification-parameter values, using, not the initial density of the cold compact, but the density after the compacts have been brought to temperature, the systematic deviations from linearity in Fig 3 and 4 might be eliminated. Such initial densities might be obtained by extrapolating the curves of Fig 1 and 2 to zero time. I am naturally pleased to see that such a very well done series of experiments leads to a heat of activation (for the densification process in hydrogen) that is much higher than that for self-diffusion, in confirmation of the less elaborate results reported by Wulff and myself (Ind. and Eng. Chem., (1948) 40, 838). J. T. KEMP*—I would like to comment on Dr. Shaler&apos;s remarks. There are apparently different interpretations of the word "sintering." It seems to me that an accurate definition of our word is essential in all metallurgy. May I point out, in this connection, that in practical metallurgy the word "sintering" has been applied to a bonding process in the preparation of ores and flue dust for fur-nacing. It would be unfortunate if in the area of powdered metallurgy we should establish a definition that is essentially different in meaning. F. N. RHINES*—I think that I can answer the question by saying that I see no essential difference between the use of the term "sintering" in extractive metallurgy and in powder metallurgy; physically the same things are going on. I admit sintering is used for different end purposes in the two cases. When we resort to the sintering of lead ore mixture we are doing so to obtain a chemically reactive, loose texture of some rigidity. This is only a difference in use. After all, in powder metallurgy we sometimes deliberately produce a very porous material which has just a little strength, just as in the case of sinter cake. P. DUWEZ (authors&apos; reply)—We agree that it would be helpful to have well-established definitions of such terms as "sintering." Since the question has now been raised, the time might be appropriate for its consideration by some suitable committee of one or more of the metallurgical societies. In answer to Dr. Shaler&apos;s first question, no getter nor hydrogen leak was used in our vacuum experiments, except insofar as the guard disks (used to reduce friction between specimens and trays) may have acted as getters. Dr. Shaler&apos;s statement that extrapolation of the curves of Fig 1 and 2 does not lead to zero densification at zero time apparently overlooks the logarithmic

Jan 1, 1950

By W. M. Robertson

The kinetics of grain boundary groove formation on copper surfaces immersed in liquid lead have been studied over the temperature range of 400° to 900°C. The groove widths were Proportional to the cube root of the annealing time, indicating that the diffusion of copper through the saturated liquid-lead solution is the mechanism by which grooves form. The rate constant for the process can be calculated by a theory due to Mullins. Using published data for the solubility of copper in liquid lead, for the interfacial energy of the solid copper-liquid lead interface, and for the diffusion coefficient of copper in liquid lead, the calculated rate constants almost exactly reproduce the measured values over the entire temperature range. The decay of scratches placed on copper surfaces has also been studied. The rate constant for scratch decay agrees with that for grain boundary groove growth, though scratch decay is sensitive to convection currents in the liquid. The interaction of solid and liquid metals has been studied extensively and has been found to be rather complex. Many of the studies have been complicated by a host of competing effects, including temperature gradients, concentration gradients, the formation of one or more intermetallic phases, natural or forced convection, and the presence in both the solid and liquid of considerable amounts of impurities and alloying elements. Recently theories have been developed of changes in surface profiles driven by capillary forces,&apos; which allow the interaction of the solid and liquid to be analyzed quite directly. The present paper reports a study of the formation of grain boundary grooves on pure copper immersed in liquid lead, which allows the theory to be checked quantitatively. The Cu-Pb equilibrium diagram is quite simple: there are no intermetallic compounds, copper is just slightly soluble in liquid lead, and lead is almost completely insoluble in solid copper.2 The Cu-Pb system has been studied extensively,3-9 and all of the quantities—interfacial energy, diffusion coefficients, and equilibrium solubilities-necessary to calculate the rate of groove growth by a volume-diffusion mechanism are known. The kinetics of grain boundary grooving and scratch smoothing have been studied on the noble metals and the iron group metals in a reducing atmosphere or in vacuum.10 The main interest of these studies has been the determination of surface-diffusion coefficients at metal-gas interfaces using the theories developed by Mullins.1 The present paper uses similar methods for the study of diffusion processes at the interface between two condensed phases. There has been one previous study" of the kinetics of groove growth in a solid-liquid system, which, however, was troubled by the fact that neither interface energies nor diffusion coefficients were known in the Ni-S system studied. THEORY The theory of grain boundary groove growth has been developed by Mullins for the cases of volume diffusion," surface diffusion," and a combination of the two processes.14 He has also analyzed the kinetics of the flattening of a scratched surface by these processes.l5,l6 Several assumptions and approximations were used in the derivations of the surface profile shapes. The applicability of these assumptions and approximations to the present system will be considered in the discussion. At the intersection of a grain boundary with an initially flat interface the equilibrium between the interfacial energy and the grain boundary energy establishes an equilibrium groove angle. This induces curvatures in the interface. The chemical potential of material at a curved interface is higher than at a flat interface, so that material moves away from the region of the grain boundary. Mullins&apos; calculations indicated that the groove profile would be similar to that shown schematically in Fig. 1. Small humps form above the level of the original flat surface. For a volume-diffusion mechanism the separation, w, of these humps at a time, t, is given by and where co is the equilibrium concentration of the solid in the liquid, y, the solid-liquid interfacial free energy, O the volume occupied by a solute atom in the liquid, D the diffusion coefficient of the solid in the liquid, and kT has its usual meaning. For a surface-diffusion mechanism the groove width is proportional to the fourth root of the time. For grooves forming by a combined surface and volume-diffusion mechanism the exponent of the

Jan 1, 1965

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By Richard F. Miller

Recent studies of creep have made it apparent that plastic deformation may occur in metals under stresses less than the elastic limit as determined from short-time tests. In summarizing conclusions drawn from creep tests by various investigators, Tapselll said: "It is evident that if a material has a true elastic range, the elastic limit must represent the maximum stress for no creep." The presence of a definite elastic limit, represented in single crystals by a critical or threshold shearing stress, is claimed by Schmid2, Elam3 and others who have investigated the plastic deformation of single crystals. However, this "law of critical shearing stress" was determined2 from short-time tests, and the measurement of the deformation was made with apparatus primarily designed to observe large amounts of plastic deformation, not to detect elastic changes. Experimental data recently obtained with highly sensitive instruments by A. W. Hanson4 on zinc and by Podaschewsky5 on rock salt indicate that the elastic range in single crystals is considerably narrower than formerly was supposed. Moreover, a theoretical possibility of permanent deformation, under the influence of even the smallest shear stress in single crystals above a certain temperature (Td), has been developed by G. I. Taylor6. This evidence seemed to warrant an examination of the elastic limit in large single crystals by means of creep tests. The first metal chosen for examination was zinc. AppaRatus The creep-testing apparatus developed for this work is shown in Figs. 1 and 2. The extensometer A is sensitive enough to detect changes in length of 3.3 X 10~6 in. per in., and yet can be used into the plastic range without injury to the apparatus. The specimen,

Jan 1, 1936

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.&apos; Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By J. Campbell

The negative pressure developed within a solidifying sphere of pure iron is investigated theoretically assuming an elastic-plastic model. The maximum hydrostatic tension attainable is shown to be an order of magnitude smaller than that required for the homogeneous muclealion of pores in the liquid cove, and four orders of magnilude smaller than that predicted from) a rigid shell model. It is well-known that liquids can withstand large hydrostatic tensile stresses, or negative pressures. The various experimental investigations of the tensile strengths (often called the fracture pressures) of liquids are reviewed by Dean,1 and the theoretical attempts at estimating fracture pressures are critically assessed by wakeshima.2 Using Fisher&apos;s3 quation, the fracture pressure of pure liquid iron is about -70,000 atm, which may be too large by as much as a factor of 4, but is certainly correct to within an order of magnitude.&apos; In view of the great importance of the problem of the nucleation of shrinkage cavities in castings it is of interest to determine exactly what tensile stresses can exist in the residual liquid in a solidifying casting; it has often been assumed that, because of the very low strengths of solid metals near their melting points, no interior stresses are developed at all. Nussey4 has determined theoretically the pressure in the liquid core of a solidifying metal sphere assuming that the solidified shell does not deform (i .e., is perfectly rigid), so that because of the contraction accompanying solidification (a) (about 3 pct for most metals) the progressive deposition of solid onto the inner surface of the shell causes the remaining liquid to be expanded to make up this difference in volume. This leads to a relation between the pressure P in the liquid, the initial pressure, PO, the bulk modulus of the liquid, K, and the inner and outer radii of the solid shell, o and b, respectively:

Jan 1, 1968

By Willis T. Burns

I. Introduction.......................................... 703 II. History................................................ 703 III. General Description of Plant......................... 704 IV. AnoDes................................................. 711 V. Cathodes............................................... 714 VI. Electrolyte............................................ 718 VII. Electrolytic Slime..................................... 727 VIII. Power................................................. 728 IX. Operating Details..................................... 732 X. Furnace Refining...................................... 736 XI. Physical Testing oF Products.......................... 739 I. Introduction. These notes are submitted, not as a discussion of the modern practice of electrolytic-copper refining, but as the record of a refinery that was among the pioneers in the field and that is to-day, and has been for 17 years, operating under conditions not to be found in any similar plant in the country. I refer to the current density, which is at least 60 per cent. higher than that regularly employed elsewhere, and to the fact that the anodes treated are the direct product of the converter rather than of the reverberatory furnace. The writer has no knowledge of any other refinery treating anodes of this character. II. History. This refinery, now one of the oldest plants of its kind operating in this country, was built in 1892 by the Boston & Montana Consolidated Copper & Silver Mining CO. to refine the product of its Great Falls reduction works. The estimated capacity of the plant as designed was 65,000 lb. of cathodes per day at a current density of 16 amperes per square foot.

Jan 1, 1914

By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,&apos; the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949

By M. C. Fuerstenau, R. B. Bhappu

The response of beryl to sulfonate flotation was examined. The dependence of flotation recovery on sulfonate concentration, pH, and the absence or presence of various ions is also demonstrated. The response of quartz and feldspar to sulfonate flotation at various values of pH is given to. show the conditions necessary for selective separation. Finally, beryl was successfully concentrated from a natural ore using a technique devised from experimental observations on systems of pure minerals. With the possible exception of quartz, the flotation characteristics of silicate minerals are rather poorly understood. This is due in part to the com- plexity of the mineral systems themselves and in part to an insufficient amount of flotation data. The complexity of the systems arises from the wide range of chemical composition that the silicate minerals can assume. This is reflected in the variability of such physical properties as hardness and cleavage. Although the chemical composition of silicate minerals can vary considerably, a general grouping can be accomplished conveniently on the basis of the assemblage of SiO4 tetrahedra in all the silicates. That is, it has been shown that six basic groups can be obtained, depending on the arrangement of oxygen sharing between adjacent silicon atoms (or substituted aluminum). When all four oxygen atoms are shared, a framework structure such as quartz or feldspar is obtained. When three oxygens are shared, infinite sheets are obtained as in the micas and clays. When two oxygen atoms of the tetrahedra are shared, infinite chains are obtained, such as those in

Jan 1, 1963

By F. A. Forward, J. Halpern

A new process for extracting uranium from ores with carbonate solutions is described. Leaching is carried out under oxygen pressure to ensure that all the uranium is converted to the soluble hexavalent state. By this method), alkaline leaching can be used successfully to treat a greater variety of ores, including pitchblende ores, than has been possible in the past. The advantages of carbonate leaching over conventional acid leaching processes are enhanced further by a new method which has been developed for recovering uranium from basic leach solutions. This is achieved by reducing the uranium to the tetravalent state with hydrogen in the presence of a suitable catalyst. A high grade uranium oxide product is precipitated directly from the leach solutions. Vanadium oxide also can be precipitated by this method. The chemistry of the leaching and precipitation reactions are discussed, and laboratory results are presented which illustrate the applicability of the process and describe the variables affecting leaching and precipitation rates, recoveries, and reagent consumption. THE extractive metallurgy of uranium is influenced by a number of special considerations which generally do not arise in connection with the treatment of the more common base metal ores. Perhaps foremost among these is the very low uranium content of most of the ores which are encountered today, usually only a few tenths of one percent. A further difficulty is presented by the fact that the uranium often occurs in such a form that it cannot be concentrated efficiently by gravity or flotation methods. In these and other important respects, there is evident some degree of parallelism between the extractive metallurgy of uranium and that of gold and, as in the latter case, it has generally been found that uranium ores can best be treated directly by selective leaching methods. It is readily evident that this parallel does not extend to the chemical properties of the two metals. Unlike gold, which is easily reduced to metallic form, uranium is highly reactive. It tends to occur as oxides, silicates, or salts. Two ores are of predominant importance as commercial sources of this metal: pitchblende which contains uranium as the oxide, U3O51 and carnotite in which the uranium is present as a complex salt with vanadium, K2O-2UCV3V2O5-3H2O. These ores may vary widely in respect to the nature of their gangue constituents. Some are largely siliceous in composition, while others consist mainly of calcite. Sometimes substantial amounts of pyrite or of organic materials are present and these may lead to specific problems in treating the ore. Further complications may be introduced by the presence of other metal values such as gold, copper, cobalt, or vanadium whose re- covery has to be considered along with that of the uranium, or whose separation from uranium presents particular difficulty. In general, there are two main processes for recovering uranium in common use today.&apos;.2 One of these employs an acid solution such as dilute sulphuric acid to extract the uranium from the ore. A suitable oxidizing agent such as MnO, or NaNO, is sometimes added if the uranium in the ore is in a partially reduced state. The uranium dissolves as a uranyl sulphate salt and can be precipitated subsequently by neutralization or other suitable treatment of the solution. The second process employs an alkaline leaching solution, usually containing sodium carbonate. The uranium, which must be in the hexavalent state, is dissolved as a complex uranyl tricarbonate salt, and then is precipitated either by neutralizing the solution with acid or by adding an excess of sodium hydroxide. The latter method has the advantage of permitting the solutions to be recycled, since the carbonate is not destroyed. This is essential if the process is to be economical, particularly with low grade ores. With each of these processes, there are associated a number of advantages and disadvantages and the choice between using acid or carbonate leaching is generally determined by the nature of the ore to be treated. In the past, more ores appear to have been amenable to acid leaching than to carbonate leaching and the former process correspondingly has found wider application. With most ores, acid leaching has been found to operate fairly efficiently and to yield high recoveries. One of the main disadvantages has been that large amounts of impurities, such as iron and aluminum, sometimes are taken into solution along with the uranium. This may give rise to a high reagent consumption and to difficulties in separating a pure uranium product. Excessive reagent consumption in the acid leach process also may result

Jan 1, 1955

By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970