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E. P. Pfleider, University of Minnesota I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. R. H. Merrill, U. S. Bureau of Mines, Denver Federal Center The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability. G. A. Leonards, Purdue University I was interested in Mr. Lane's observations concerning the correspondence between rate of slide movement with rise of reservoir. Perhaps the most interesting feature is that the rate of movement at the time the rock slope failed was less than the rate at an earlier time when it did not fail. This is difficult to explain from current slope stability theory. K. S. Lane, U. S. Army Corps of Engineers I believe that reduced rate of movement is the result of the progressive type of failure, such as described by Patton and Deere. which occurs along the sliding surfaces. It is difficult to analytically define the progressive failure condition for inclusion in slope stability conditions, but its existence should be recognized in design. We should also realize that many apparently stable slopes undoubtedly contain overstressed regions. To design a slope with no overstressed region would be uneconomical and conservative. D. H. Deere I would pose the question-"What is the meaning of a factor of safety of one?" We were involved in the design of a large, irregularly shaped, underground cavity with an unsupported span of several hundreds of feet. Tests on rock specimens indicated a strength of 1300 lb per sq in. The RQD would have been between 90 to 100 percent indicating excellent structural continuity. In-situ stress determinations indicated an approximately hydrostatic state of stress at a level of 1400 lb per sq in. Calculation of stress concentrations at the walls indicated that the stresses there would be about 3000 to 4000 lb per sq in. Admittedly the rock is in a confined condition everywhere except at the very skin of the wall and the rock walls would thus on the average be somewhat stronger. Allowing for the effect of restraint the factor of safety was found to be less than 0.5 over a region several feet into the wall. Construction was started, using rockbolts only to support the walls. Failure around the immediate skin occurred after each

Jan 1, 1967

By D. Turnbull

RECENTLY it has been shown that aggregates of small liquid droplets of tin,' mercury' or gallium' kept from intercommunicating by suitable films do not solidify at an appreciable rate unless the supercooling is very much greater than that usually necessary to cause a large continuous mass of the metal to solidify. For example oxide-coated tin droplets1 (1 to 10 micron diam) must be supercooled 100" to 110°C before their rate of solidification becomes rapid, although large continuous masses of liquid tin usually begin to solidify when supercooled 30" or less." These experiments have been interpreted' on the hypothesis that nucleation of crystals in large continuous metal samples is almost always catalyzed by accidental inclusions. Therefore, if the metal is dispersed into a number of isolated droplets large in comparison with the number of inclusions, most of the droplets should not crystallize until a temperature sufficiently below the thermodynamic melt- ing point, T0, has been reached to permit an ap-preciable rate of homogeneous (noncatalyzed) nu-cleation. In general this temperature is very much less than the temperature at which the rate of heterogeneous (catalyzed) nucleation is appreciable. If this interpretation is correct then investigation of the kinetics of crystallization of small droplet aggregates should be one of the most fruitful methods of obtaining information about the homogeneous formation of crystal nuclei in liquids. In this paper the results obtained on gallium and mercury are reported more fully. In addition, results on the supercooling of aggregates of liquid bismuth and lead droplets are included. Experimental Procedure Some care must be exercised in the choice of a barrier to prevent the liquid droplets from coalescing lest the barrier itself catalyze the formation of crystal nuclei. From this standpoint, the most desirable barrier is vacuum or inert gas, but, because of the difficulty of experimental arrangement, solid compounds and adsorbed films have been selected. There are two guiding principles in the selection of compounds as barriers in addition to the requirement that they prevent coalescence of liquid droplets. First, the compound should be almost insoluble in the liquid metal and second, its lattice structure should be quite unlike that of the forming metal crystal. Even so, there is no a priori assurance that the solid compound film will not catalyze to some extent the formation of metal crystal nuclei. An adsorbed protective monolayer is less likely to be catalytic than a crystal compound film, but it is not often possible to find a monolayer that is stable under the experimental conditions. Also, it is desirable, though not generally essential, that the aggregate of droplets be prepared by breaking up the massive metal rather than from a powdered compound of the metal.

Jan 1, 1951

By L. D. Ricketts

Discussion of the paper of L. D. RICKETTS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 100, April, 1915, pp. 711 to 737. FREDERICK LAIST, Anaconda, Mont.-I am going to tell you of some of the results we have been getting in Anaconda during the past two or three months in a large plant which was finished in May. We commenced work in Anaconda a year and a half ago on the construction of a leaching plant which was to have a capacity of 2,000 tons per day. The plant was to treat tailings from the concentrator, containing about 12 1b. of copper to the ton. During the past year we changed our plans and decided to use the flotation process on the tailings from the concentrator, which contained no oxidized copper, and apply the leaching process only to tailings which had accumulated in a large dump below the works. This dump contains about 15,000,000 tons of tailings, and since some of the copper in it is oxidized, we felt that the application of the flotation process would result in the loss of too much of the oxidized copper, particularly as time went on. In starting up we had a number of difficulties to overcome, as is usually the case. They were not of a serious character. The results obtained, so far, have been decidedly encouraging. During July the plant treated a total of 50,000 tons of tailings, or an average of 1,610 tons per clay. The extraction was about 83 per cent., which, on material of the grade treated, meant a. tailing assaying under 0.1 per cent. copper. The acid consumption was about 65 lb. per ton, and the fuel percentage in. roasting was about 4 ¼ . We expect to cut the fuel percentage in the next month or two to about 3 per cent., the high percentage during July being clue to starting up and shutting clown furnaces. We find that iron builds up in the solution to a marked degree. This is not a serious platter with us, because we have cheap sulphuric acid and can reject solution whenever it gets too foul. The extraction of silver has been remarkably good in the large plant. It has averaged better than 75 per cent. It seems that so long as we maintain salt in the solution to a percentage of 10 per cent., the extraction is good. We allowed the salt to fall off in order to find how low a percentage we could use. At about 7 per cent. the silver extraction fell to 65 per cent. This was to be expected, because silver chloride is soluble in strong brine, but not in weak brine.

Jan 12, 1915

By J. D. Clark

ONE'S lifetime does not usually offer the oppor-tunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool. Mineralogy Petalite is a lithium-aluminum-silicate mineral. It was from petalite that J. A. Arfwedson first discovered lithium in 1818. The theoretical composition of Li2O • A12O8 • 8SiO2 is equivalent to 78.4 pct silica, 16.7 pct alumina and 4.9 pct lithia. The mineral in its known commercial occurrence is colorless to white and rarely gray, transluscent and rarely transparent. It is brittle, has a vitreous luster, and occurs usually in cleavable masses (fig. 1). It is classified as a di-silicate, but is similar in composition to the metasilicate spodumene, Li2O.-Al2O8-4SiO2 (table I). However, their specific gravities are quite different (3.13 to 3.20 for spodumene, 2.39 to 2.46 for petalite). Occurrence Petalite specimens have been reported in many localities; however, there are only three known countries having occurrences of commercial significance. The classic locality is Sweden's Utö Mines, which, although reportedly still containing considerable petalite, have been closed and are not expected to be operated in the near future. At Varuträsk, in northern Sweden, petalite carrying 4 pct lithium oxide is the main ore. In 1946 there was reported about 1000 tons on hand. However, the iron content was 0.60 pet too high for other than chemical use. Petalite has been reported in western Australia. At the Cottesloe mine, where small quantities have been reported available, it is produced in conjunction with feldspar. Petalite occurs in considerable quantity in the feldspar quarry at Londonderry, and it was estimated1 in 1943 that over 3700 tons might be available. The petalite in South West Africa was first discovered by F. J. Jooste, a lawyer by profession, in 1938. The following year he discovered a much larger deposit, and in 1948 another important discovery was made. These deposits occur near Kari-bib and constitute the only known commercial deposits. Their full extent has not yet been determined, but huge massive blocks of petalite of the purest grade, running into many thousands of tons, can be seen in all these deposits. To date, 60,000 tons of high grade, low iron containing ore has been blocked out in the major bodies. Mining for years to come will be confined to simple quarrying. Selection from accessory minerals has proved

Jan 1, 1951

By J. D. Clark

ONE'S lifetime does not usually offer the oppor-tunity to observe and be a part of the commercial development of an entirely new material. Petalite has been known for over a century, but at first it was presumed rare. However, it was found to be so abundant that it has become a new and extremely useful industrial tool. Mineralogy Petalite is a lithium-aluminum-silicate mineral. It was from petalite that J. A. Arfwedson first discovered lithium in 1818. The theoretical composition of Li2O • A12O8 • 8SiO2 is equivalent to 78.4 pct silica, 16.7 pct alumina and 4.9 pct lithia. The mineral in its known commercial occurrence is colorless to white and rarely gray, transluscent and rarely transparent. It is brittle, has a vitreous luster, and occurs usually in cleavable masses (fig. 1). It is classified as a di-silicate, but is similar in composition to the metasilicate spodumene, Li2O.-Al2O8-4SiO2 (table I). However, their specific gravities are quite different (3.13 to 3.20 for spodumene, 2.39 to 2.46 for petalite). Occurrence Petalite specimens have been reported in many localities; however, there are only three known countries having occurrences of commercial significance. The classic locality is Sweden's Utö Mines, which, although reportedly still containing considerable petalite, have been closed and are not expected to be operated in the near future. At Varuträsk, in northern Sweden, petalite carrying 4 pct lithium oxide is the main ore. In 1946 there was reported about 1000 tons on hand. However, the iron content was 0.60 pet too high for other than chemical use. Petalite has been reported in western Australia. At the Cottesloe mine, where small quantities have been reported available, it is produced in conjunction with feldspar. Petalite occurs in considerable quantity in the feldspar quarry at Londonderry, and it was estimated1 in 1943 that over 3700 tons might be available. The petalite in South West Africa was first discovered by F. J. Jooste, a lawyer by profession, in 1938. The following year he discovered a much larger deposit, and in 1948 another important discovery was made. These deposits occur near Kari-bib and constitute the only known commercial deposits. Their full extent has not yet been determined, but huge massive blocks of petalite of the purest grade, running into many thousands of tons, can be seen in all these deposits. To date, 60,000 tons of high grade, low iron containing ore has been blocked out in the major bodies. Mining for years to come will be confined to simple quarrying. Selection from accessory minerals has proved

Jan 1, 1951

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

Phase diagrams for the Ti-W and Ti-Ta systems were determined. The Ti-W system is characterized by a wide, two-phase region of ß plus tungsten which is derived from a peritectic reaction between the liquid and tungsten solid solutions. The ß field terminates in a eutectoid reaction between a titanium and tungsten terminal solid solution. Tantalum and ß titanium form a complete series of solid solutions. Other features of this system are the extensive a-ß field at low temperatures and an appreciable solubility of tantalum in a titanium. BOTH tungsten and tantalum were first thought to form ß-isomorphous systems with titanium as a result of early work' using powder-metallurgical techniques. Later work2 on arc-melted Ti-Ta alloys, made using a commercial titanium base, showed that, in the range of 0 to 10 pct, tantalum was soluble in ß titanium and that the a solubility extended to between 2 and 5 pct Ta at 790 °C. The present investigation covered the entire alloy range in both systems and was chiefly concerned with high-purity alloys at the titanium-rich end. The constitution of titanium-rich alloys made with a commercial titanium base was reported by Holla-day, Kura, and Jackson.3, 4 As will be shown in detail later, the early prediction of a isomorphism was true for the case of the Ti-Ta system, but not for the Ti-W system. The results of this investigation will be presented first. The experimental methods used are described in the Appendix. Ti-W System The entire Ti-W phase diagram is shown in Fig. 1. Details of the titanium-rich side are shown in Fig. 2. The chief features of the system are a ß eutectoid and a high-temperature peritectic between liquid and tungsten solid solution. Melting Range: Examination of cast structures of low and medium-tungsten-content ingots showed cored ß phase as the primary constituent. Fig. 3a illustrates a typical cast structure for alloys in the range of 20 to 30 pct W. From 30 to 72 pct W, coring was very severe. Alloys containing 72 through 88 pct W, however, showed definite evidence of a peritectic reaction between the liquid and a terminal solid solution of titanium in tungsten. Fig. 3b shows the cast structure for an 80 pct W alloy. A 95 pct W alloy, shown in Fig. 4, consisted primarily of primary tungsten solid solution plus a small quantity of ß probably rejected during cooling. Incipient-melting experiments located the peritectic temperature between 1850" and 1900°C and indicated that the reacting phases are liquid containing about 25 pct W and tungsten terminal solid solution containing about 8 pct Ti. Figs. 5 and 6

Jan 1, 1954

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By C. W. Volek, G. Mandl

Steam-injection tests in the field have shoum that heat transport into the oil/water region, ahead of the steam zone, may have a significant effect on the production process. Earlier theoretical work on reservoir heating by hot-fluid injection can be used to describe the growth of the steam zone, but only if heat transport from steam zone into oil/water region is neglected. It therefore became necessary to re-examine and extend the earlier theory. It was found that this theory ceases to be consistent with the physical model of the process at a certain critical time, tc, which depends on reservoir thickness, temperature, and quality of the steam. The critical time marks an important change in the heat flow across the condensation frovt: the heat flow, which is purely conductive during 0 < t < tc&apos; becomes predominantly convective at t = tc. Accordingly, at t = tc, the equation which governs expansion of the steam zone changes. On the basis of the new equation, an approximate description for the steam-zone growth during t > tc is developed by making use of upper and lower bounds for the exact solution of the problem. The boundary conditions for heat and mass flow inside the oil/water region are established, and a simple method of detennining the saturation at the downstream side of the condensation front is presented. Experimental results show that the theory gives an accurate description of steam-zone expansion before the critical time. At times near critical time, and also after critical time, experimental data show theoretical steam-zone volumes to be high. Even so, the accuracy of the calculated steam-zone volumes is sufficient for practical purposes. THEORY OF STEAM-ZONE GROWTH INTRODUCTION The engineering evaluation of steam-drive processes is based mainly on a mathematical description of reservoir heating by hot fluid injection presented several years ago by Marx and Langenheim.l This theory can be used to determine the growth of the steam zone,2 provided the flow of heat from the steam zone into the liquid zone ahead of the condensation front (Fig. 1) is neglected. Since we must expect, however, that heat transport into and inside the liquid region (the region between condensation front and production wells) will affect both the water/oil flow and the growth of the steam zone, it is necessary to re-examine and to generalize the Marx and Langenheim theory as applied to steam drive, which will hereafter be termed the "old" theory. Observations made in several field tests emphasize the need to study the heat flow across the condensation front (CF). On several occasions it was discovered that heat was transported in the liquid zone far ahead of the advancing CF, resulting in an early breakthrough of warm water. This seems to occur most often when high injection pressures are applied, when "wet" kONINKLIJKE/SHELL EXPLORATIE EN PRODUKTIE LABORATORIUM RIJSWIJK, THE NETHERLANDS SHELL DEVELOPMENT CO. HOUSTON, TEX.

Jan 1, 1970

By C. E. Sims, H. M. Banta, S. L. Hoyt

OVER the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking specifically underbead cracking, or "hard cracks," or parent-metal cracks-is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.1 The tests described are made under restraint to facilitate cracking and, are so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when arc-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking. tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institute 0n two projects, one

Jan 1, 1945

By D. W. Mitchell

While pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)&apos; the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superhcating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is mis-cible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetal-lic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck³ states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron -would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones% ho studied the physical properties of low iron magnesium alloys observed a 57°

Jan 1, 1949

By A. W. H. Morris, E. A. Steigerwald

The jatzgue beizazriov oj Mietal matrix co))zpos~tes in tension -lensiom loading has been imestigated as a junction of Dolume fraclion veinfovcelnent using the model systems of a silver matrix reinforced with contlnuous or dzscontztinuous aligned tungsten jilamenls and continuous aligned steel filamenls. Appreciable impvocetnents in fatigue strength were obseved in all syslems inzvesLigated, the degree of sl renglhenng-increasing with increasing volume fraclion of reinforcement. The mode of fatigue failure was found to be a function of colutrre jp-actiotz and was also noted to be controlled by the relative fatigue and strength characlerislics of the matrix and reinforcemenl. THE advantages to be gained by suitably incorporating high-strength filaments or whiskers into metallic matrices are well-recognized.&apos; To date emphasis has been placed on the experimental determination of tensile strengths and elastic moduli of metal matrix composites measured parallel to unidirectionally aligned filaments. Several attempts have been made to relate experimentally measured tensile properties to theoretical values calculated from the properties of the components on the basis of the relatively simple "rule of mixtures" analysis. However, relatively few data have been reported in the literature on the fatigue behavior and mechanism of fatigue failure of metal matrix composites. In a study of fatigue crack propagation in aluminum plus steel wires and aluminum plus tungsten wires, Forsyth et a1.2 found that the incorporation of small numbers of filaments suitably dispersed were capable of substantially reducing the rate of fatigue crack propagation. For this purpose, the strength of the filaments appeared to be more important than the aspect ratio and the authors reported that parallel filaments were not the most favorable orientation for increased strength. In a basic study of the fiber reinforcement of metals, Williams and 0&apos;brien3 report preliminary results which indicate a considerable improvement in fatigue strength in reversed bending fatigue of a steel wire-reinforced aluminum alloy composite. In a study of the influence of interfacial bonding on fatigue behavior, Baker4 has also reported improved fatigue properties in stainless steel-reinforced aluminum composites. In contrast, Ham and place5 report that, although tensile properties are improved greatly by filament reinforcement, the reinforcement of copper with continuous, brittle tungsten wires up to 23 vol pct was comparatively ineffective against fatigue. The authors attribute the poor fatigue properties of the composite to fatigue hardening of the matrix at the tips of cracks which can build up stress concentrations sufficiently large to fracture proximate filaments. Baker and cratchley6 failed to find marked improvements in the reversed-bending fatigue properties of silica-reinforced aluminum. The study was complicated by the complex behavior in a composite during the compres-sive half-cycles imposed in this type of loading. This was manifested in the failure of the composites by de-lamination, a contributing factor being the presence of aluminum oxide at the matrix-filament interface. Prior to the general acceptance of filament-rein-

Jan 1, 1968

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By R. S. Craig, W. E. Wallace, G. S. Kamath

The destruction of long-range order in Mg-Cd, has previously been thought to occur as a second order process. In the present work a variety of X-ray diffraction techniques are employed to show that in this case and in Mg-Cd alloys containing frorn 20 to 33 1/3 at. pct Mg the process more nearly resembles an ordinary first order phase transformation. It is found that the ordered alloy, which occurs as a single phase at lgw temperatures, transforms with increasing temperature into a Cd-enriched disordered (P) phase and an Mg-enriched ordered (a) phase. The interval over which these two phases coexist under apparently equilibrium conditiovs extends from 25" to 87°C content. At 33 1/3 at. pct Mg the two-phase region has disappeared. Measurement of the long range order parameter, s, for the ordered phase in MgCd, (from superlattice line intensities) shows that it disorders only very slightly before it is transformed into the p form. Kinetic experiments reveal that when the a phase is formed frorn the p phase by suitably quenching so as to suppress phase segregation, the transformation is essentially complete and the a phase has acquired its equilibrium value of S in less than 1 min. In an earlier investigation carried out in this Laboratory1 the rate of disordering of the MgCd3 superlattice was determined over an extensive range of temperature. The process was found to be first order and the rate constant, k, was established. At the lowest temperatures studied k was found to increase exponentially with temperature. At higher temperatures, however, it passed through a maximum and for the 100 deg interval below the point at which the superlattice was destroyed k was observed to decrease with increasing temperature. The various theoretical treatments1-3 of order-disorder phenomena lead to a negative temperature coefficient for k near the superlattice critical temperature but this region for MgCdB seemed unusually wide. Detailed analysis of the point indicated&apos; that either the long-range order parameter, S, for MgCda varied with temperature in an anomalous way or the disordering in this instance is more complex than in the cases which have been treated theoretically. The original objective in the present work was simply to determine S vs temperature for MgCda to ascertain whether the disordering was in conformity with theoretical expectations.2° In an early stage of the work it was noted, however, that under equilibrium conditions ordered (a) and disordered (0) phases coexist in MgCd, over a considerable range of temperature. Since on thermo- dynamic grounds the coexisting phases must differ in composition, the investigation was enlarged to permit the compositions of the two phases in MgCd3 to be determined and to establish the extent of the two phase regions for alloys containing from 20 to 33 1/3 at. pct Cd.

Jan 1, 1963

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962

By Robert E. Green

Formulae are given for calculating the modes of wave propagation in a single-crystdl specimen possessing a given crystallographic orientation. Such calculations lead to determination of the orientation factor appearing in the Granato-Lucke theory for the attenuation of these waves due to dislocation damping. A detailed treatment is given for the case of an aluminum crystal possessing the orientation having a maximum Schmid fac -tor of 0.5. FOR a number of years the attenuation of ultrasonic waves propagating in metals has been used to investigate various phenomena causing internal friction.Most of the experiments were performed on polycrystalline test specimens and the waves were assumed to be propagating in an isotopic medium. However Alers 6 in 1955 and more recently Hikata et at. Chiao and Gordon,8 and Swanson and Green 10 have used measurements of attenuation of ultrasonic waves to study internal-friction changes in single crystals. These authors were concerned with the energy losses experienced by the ultrasonic waves due to dislocation motion induced by plastic deformation of the crystals. Alers measured the attenuation of 7 mc per sec ultrasonic pulses propagating in zinc single crystals before, during, and after plastic deformation. Simultaneously he measured the time-dependent plastic strain at constant stress in order to study the correlation between this strain and attenuation. The crystals were oriented in such a way that the applied stress provided a direct shear on the slip plane, thus causing the deformation to proceed by slip on this plane. At the same time the high-frequency sound pulses were sent through the crystal perpendicular to the slip plane. He found that the attenuation of transverse waves, the stress vectors of which lie in the slip plane, was very sensitive to the deformation. The polarization of the particle displacements, associated with these waves, relative to the applied static shear stress, and hence the direction of slip, had no obvious effect on the results. The attenuation of longitudinal waves was affected by the deformation only when the slip plane was not perpendicular to the propagation direction. This indicated that the attenuation was caused by dislocations introduced by the deformation and moving only in the slip plane. Hikata et al. made simultaneous measurements of attenuation, velocity changes, and stress-strain relations on aluminum single crystals deformed in tension. Both longitudinal and shear waves were used, at frequencies of 10 and 13 mc per sec. They placed emphasis on the choice of propagation modes and polarization of the ultrasonic waves, such that interactions between these waves and dislocations on selected slip systems could be investigated. They also selected specimens possessing specific crys-tallographic orientations, which allowed investigation as a function of the number of equally favored slip systems under the applied stress. They found that, for symmetrical orientations, the change of attenuation decreases with the increasing number of equally favored slip systems, i.e., in the order

Jan 1, 1964

By Nicholas J. Grant, William H. Ferguson, Bill C. Giessen

Ta-lr alloys have been examined over the complete range of compositions using metallographic and X-ray techniques. The terminal solid-solubility limits, solidus temperatures, and intermediate phases were determined. There are four inter-mediate phases: o, tetragonal, analogous to a (Fe-Cr); 0,. orthorhombic; az, tetragonal; and a TaZr,, cubic, AuCu, structure. Of these, o and a, melt peritecticaLly, a, decomposes peritectoidally, and a TaIrs has a congruent melting point. Three peri-tectic and one eutectic reactions occur. 1 HE Ta-Ir phase diagram has not been treated in the literature. Intermetallic phases and terminal solid solubilities have been described and estimated.&apos;-4 The previous findings have been confirmed in this work. A complete diagram with additional phases and solidus curves is presented. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by the National Research Corp., Cambridge, Mass., and iridium powder of 99.9 pct purity, supplied by the Bishop Co., Malvern, Pa. Both powders were -200 mesh. Table I lists the analyses as given by the suppliers. A standard procedure was employed in making the alloy buttons, which was described in detail in Refs. 5 and 6, and which included repeated arc-melting of powder compacts and determination of the composition by the weight-balance method. This is especially justifiable due to the similar vapor pressures of tantalum and iridium. In the critical parts of the diagram, a spacing of 1/2 at. pct was used, based on premelted master alloy material. The observed structures and X-ray spectra were consistent with the composition sequence of the alloys. Table II lists the final alloy atomic percentages with the calculated percent error of composition. Cross sections representative in grain size and composition were selected for the study, as described in Ref. 5. Based on prior experience, no contamination from the tungsten electrode was considered. Temperature measurements were obtained using a Leeds and Northrup optical pyrometer and have been described extensively in Refs. 5 and 6. All heat treatments were made in the high-vacuum tantalum tube furnace mentioned in Ref. 5. Samples annealed in tantalum containers cooled from 1800" to 1000"~ in 5 sec; those annealed in ceramic crucibles cooled over the same range in 15 to 30 sec. The thermal treatments are listed in Table 111. All specimens were homogenized at 1735°C for 24 hr. Tantalum-rich compositions were treated in tantalum buckets. Iridium-rich compositions were annealed in tantalum buckets below the eutectic temperature of 1950°C; up to 2200°C, tungsten-lined tantalum baskets were used; and above 2200°C thoria crucibles were used. It was found that refractory oxides (in early stages of the investigation alumina crucibles were used up to 1800°C and thoria crucibles were used to 2400"~) give off minute amounts of oxygen and thereby influence the microstructure considerably, or react directly with the alloys.

Jan 1, 1963

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute. Since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1° to 2°C. per min. with or without slow stirring (Fig. 1). By this method the lead-rich end of the lead-antimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the&apos; liquidus curve of the .binary alloys did not intersect at the eutectic temperature. An equivalent effect was observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent investigation by Pellini and Rhines,1 who determined the eutectic temperature to be 251.5°C. The observation that the curves of primary crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomenon by assuming the existence of a compound Sb4Pb. He felt that super-cooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3. the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature of 250° to 252°C. at a rate of cooling of about 6°C. per min. Abel, Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous, publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic contains only 11,4 to 11.5 per cent antimony. (Previous analyses by Stead4 in 1881 gave 13 per cent:) Weaver," however, reported in 1935 that cooling curves indi-

Jan 1, 1943

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"&apos; the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,&apos; and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,&apos; or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.&apos; A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951