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By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962

By T. E. Leontis, D. H. Feisel

MAGNESIUM alloys containing rare earth metals have received considerable attention during the past several years because of the need for light alloys having high strength and creep resistance at elevated temperatures. Although much of the work reported earlier has dealt with alloys containing Mischmetal, it has been shown in two previous papersl, V hat distinctly different effects are produced by various rare earth metals and rare earth metal mixtures on the properties of magnesium. For example, much higher strengths are obtained in magnesium alloys containing didym-ium (essentially neodymium plus praseodymium) than in alloys made with Mischmetal, which contains all the rare earth metals in the proportions in which they occur naturally in the monazite ore. Mg-rare earth metal alloys are characterized by a relatively coarse grain size, which greatly impairs castability. The addition of zirconium as a second alloying ingredient has been shown8,7 to refine the grain size, which also produces a distinct improvement in the strength properties. Certain Mg-Mischmetal-Zr and Mg-Mischmetal-Zn-Zr alloy compositions which are currently being produced commercially have been discussed in dytail by Nelson and Strieter,8,4 who also present some in- formation on a Mg-low Ce-Mischmetal-Zr alloy, and by Nelson.8 A patent issued to Jessup, Emley, and Fisher9 emphasizes the superiority of Mg-didymium-Zn-Zr alloys over the corresponding alloys made with Mischmetal. The purpose of this paper is to present the results of an extensive investigation concerned with the effect of increasing amounts of zirconium on magnesium sand casting alloys containing several different rare earth metal mixtures in varying amounts. The effect of the addition of zinc to some of these alloys is also being reported. Preparation and Testing of Alloys The alloys studied in this investigation were prepared in small laboratory melts according to the melting procedures described by Nelson1" as the Crucible Method. Electrolytic magnesium having the composition shown in Table I was used as the starting material. The rare earth metal alloying ingredients used in preparing these alloys were essentially of the compositions listed in Table 11. Some of the didymium-containing alloys were prepared using a Mg-didymium hardener. The rare earth metal content of this hardener analyzed 1.2 pct Ce, 10.4 pct Pr, 80.8 pct Nd, and 7.6 pct La. The zirconium was added in one of three forms: 1) as sponge zirconium obtained from the Bureau of Mines; 2) as a fused salt consisting of 50 pct ZrCl, and 50 pct alkali chlorides from which the zirconium is reduced by the magnesium; or 3) as a Mg-Zr hardener. The alloying procedures and melt hand-

Jan 1, 1958

By G. E. Tardiff, A. A. Hendrickson

THE objectives of this communication are to present the solid-solution strengthening data for silver-base zinc single crystals and to evaluate the importance of strength contributions from several mechanisms through the use of this data combined with that for the silver-base aluminum case.' Some features of the yield point behavior of silver-base zinc crystals were previously reported.' Silver-base zinc alloys were prepared by induction melting 99.99 pct Ag with 99.9 pct Zn in high-purity graphite crucibles contained in argon-filled quartz tubes. After the first melting, the ingots were cut into short lengths, redistributed in the molds, and remelted in order to reduce solute-concentration variations. Alloy single crystals were then grown from the melt through the use of a modified Bridgeman technique which consisted of lowering the graphite crystal mold through a hot zone at a rate of 3/8 in. per hr. As in the melting operation, the molds were contained in argon-filled quartz tubes. Gage lengths 2 cm in length were introduced by both spark machining (circular cross sections) and abrading and acid etching (rectangular cross section) followed by electropolishing (a comparison of the critical resolved shear-stress values prepared by the two techniques showed no differences in strength values). The final cross-sectional areas of the crystals were approximately 5 sq mm. Prior to testing, the crystals were annealed at 600°C for 20 hr in argon atmospheres, furnace-cooled, and lightly electropolished. Crystal orientations were determined using the back-reflection method. The tensile testing was done on a Model FM Instron at a strain rate of 1(T4 per sec. Test temperatures of 77", 200°, and 400°K were attained by immersing the specimens in liquid nitrogen, dry ice-acetone mixtures, and silicone oil, respectively. The critical resolved shear-stress (CRSS) values for silver-base zinc crystals as a function of composition and testing temperature are given in Fig. 1. It will be noted that the CRSS for silver-base zinc solid solutions, as in the silver-base aluminum1 case, depends on temperature in a manner typical of fcc solid solutions: at high temperatures (-300°K and above), the CRSS is relatively temperature-independent but becomes strongly dependent on temperature at lower testing temperatures. A reasonable picture of solid-solution strengthening for silver-rich solutions at room temperature based on "direct" strengthening mechanisms3 is as follows. Since silver alloys have low stacking-fault energies, extended dislocations are expected and it is possible that Suzuki locking4 makes the major contribution to the room-temperature solute strengthening. This provides essentially temperature-independent strengthening since thermal motions of the dislocation line are not large enough to aid the dislocation in escaping the solute atmosphere extending over the fault width. An estimate of the

Jan 1, 1964

By M. D. Hassialis

THE claim is made in a number of patents1,2,3,4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S¬R[=]-R’ (where x = r,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using Biphenyl sulphide, ditolyl disulphide and dinapthyl disulphide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed was that of Moses, Hess, and Perkins. A sample of ore weighing 500 grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a 2-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8: 1. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of 12: 1. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. CONTACT-ANGLE TESTS In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcocite, chalcopyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By Walter E. Duncan

THE ores treated at the concentrating plant largely come from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately intergrown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four concentrates: (I) lead concentrates, (2) zinc concentrates, (3) acid-grade fluorspar concentrates and (4) metallurgical-grade fluorspar concentrates.2,3 Although fluorspar had been floated in Canada in 1921 4 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Mines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; such as, for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1946

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 William Klement

THIS note reports the results of some attempts to metastably extend the primary solid solubilities of tin, antimony, and silicon in silver by rapidly quenching these binary alloys from the melt. The procedures employed for alloy preparation, quenching, and Debye-Scherrer X-ray diffraction measurements have been described elsewhere. The lattice parameters obtained for the fcc structures in Ag-Sn and Ag-Sb alloys are presented in Fig. 1, together with the results of Owen and Roberts.4 Alloy compositions are believed to be within ± 0.2 at. pct on the basis of negligible weight losses during preparation and reproducibility of the lattice spacings. Diffraction lines from hcp phases were also detected: the relative visual intensities of the fcc (200) and hcp (10.2) lines were estimated as shown in Table I. The intensities were m for the (200) and w for the (10.2) in a quenched 13.6 at. pct Sn alloy: a lattice spacing for the fcc structure could not be reliably obtained, however. As seen from Fig. 1, the lattice parameters vary linearly with composition up to 8., at. pct Sb and 13." at. pct Sn, respectively, which may be compared with the maximum equilibrium solid solubilities5 of 7.2 at. pct Sb and 11.5 at. pct Sn, respectively. The presence of the hcp phases, which were found together with the fcc phases, is a consequence of the competition1,3 in the nucleation and growth processes during solidification. Both the fcc and hcp phases must be of the same composition for those alloys in the range where lattice parameters increase linearly with solute concentration. Despite much effort with quenched alloys of several silicon concentrations, it has not been possible to obtain lattice spacings of sufficient precision to establish the variation of lattice parameter with composition or the maximum metastable solid solubility: the equilibrium data5 suggest little primary solid solubility of silicon in silver. For alloys containing less than 16 at. pct Si, the Si (111) diffraction line was not observed. For alloys containing 10 to 25 at. pct Si, faint low-angle lines were detected and these could be indexed as the (10.0), (00.2). and (10.1) reflections of an hcp structure with a = 2.87 + 3A. c = 4.52 ± 3A, and c/a = 1.57 ± 2. The 16 at. pct Si alloy was quenched to, and examined at. liquid nitrogen temperatures without any change observed in the proportion of the hcp phase. These experiments were jointly supported by the Atomic Energy Commission and Office of Naval Research under a program directed by Professor P. Duwez. The assistance of H.-L. Luo and A. Abu-Shumays is acknowledged. as is the support afforded

Jan 1, 1965

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By George P. Chapman

Mica is a platy mineral occurring in a variety of complex hydrous aluminosilicate forms with differing chemical composition and physical properties. Principal minerals in the mica group include: Muscovite-potassium mica (colorless or pale green/ ruby) Phlogopite-magnesium mica (dark brown or amber) Biotite-magnesium-iron mica (black or dark green) Lepidolite-lithium mica (lilac) Selected properties are given in Table 1. Muscovite is most important commercially with phlogopite of lesser use. The laminated structure of mica enables it to be split into very thin films which are transparent and tough as well as having outstanding dielectric and insulating properties. Commercially, mica is used in a number of forms (Chowdbury, 1941; Rajgarhia, 1951; Skow, 1962). Sheet mica consists of flat sheets mined from naturally occurring books of mica, free from defects and capable of being punched or stamped into required shapes. Sheet mica is separately classified into blocks, films, or splittings according to thickness. Built-up mica, or micanite, is made by arranging overlapping splittings in layers , cemented with a binder and pressed together at high temperature. Reconstituted mica, or mica paper, is made by depositing fine flakes of high-quality scrap mica in a continuous film impregnated with binder. Scrap and flake mica are normally unsuitable in quality or size for making sheet mica. Originally the term scrap mica referred to the waste byproduct of mining and fabricating sheet mica, and distinct uses were developed for this material. Subsequently it became economically feasible to mine lower quality mica for these uses, and the term flake mica was introduced. Although the two terms are still used somewhat synonymously, it is considered better, at least in the United States, to use the term flake mica in referring to mica mined for uses other than as sheet mica; and to restrict the term scrap mica to mica mined for or with sheet mica, but which will not meet the specifications. Synthetic mica, such as fluorophlogopite, is produced by slow crystallization of a melted blend of pure raw materials. Mineralogy In the true sense the term mica does not relate to, a particular mineral, but to a group or family of minerals of similar chemical composition and to some extent similar physical properties. These minerals are predominantly potassium aluminum silicates with varying amounts of magnesium, iron, and lithium. The precise formulas and isomorphic relationships of the various group members have been studied, but general agreement has not been reached (Grimshaw, 1971; Hurlbut, 1952; Skow, 1962). The general formula describing the chemical composition of micas is [X2Y4-6Z8020(OH, F)4, where X is mainly K, Na, or Ca; Y is mainly Al, Mg, or Fe; Z is mainly Si or Al (Deer, et al., 1962).] These minerals have an internal structure of the layered lattice type where the silicon atoms are in the center of a tetrahedral grouping of oxygen atoms. The groups are linked together in a single plane by three oxygen atoms that lie within the common plane. Each of these oxygen atoms is shared by two tetrahedra. These linked tetrahedral groups, when continually extended, produce a hexagonal network within the plane. This internal structure of the mica has been used to explain the ex-

Jan 1, 1983

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By N. F. Fiore, M. C. Mangalick

DISLOCATION damping in single crystals is orientation dependent.&apos; If dislocations are distributed uniformly over all the slip systems in a crystal, and if each dislocation contributes identically to the damping process, then a damping loss or decrement 6 arises. In fact, however, for a crystal of axial direction (hkl), dislocations on certain slip systems are oriented to make a larger contribution to the damping loss than are dislocations on other slip systems. Thus the measuring damping, 6 (hkl) is proportional to an orientation factor (hkl), which weights the ability of each slip system in the crystal to contribute to the total damping. If it is assumed that dislocations are distributed uniformly on all slip systems, then for a given orientation of an fcc crystal this factor is determined2,3 by the three nonzero elastic constants Cll, C12, and C44 and the density p. In this communication measured values of elastic constants for two Fe-18Cr-Ni alloys are reported, and the dislocation damping results on two different orientations of each alloy are analyzed for orientation dependence. Elastic constants were determined by measuring the ultrasonic velocities of one longitudinal and two shear waves in (110) direction of the fcc crystals.4 Variation of velocities with the change in orientation is very small for (110) orientation,3 and so this direction is ideal for orientation factor and comparative damping measurements. Experimental Procedures. The nominal compositions of the alloys studied are given in Table I. These alloys were vacuum-melted and vacuum-cast from high-purity materials at U.S. Steel Applied Research Laboratories. The single crystals were grown by the modified Bridgeman technique. The specimens were homogenized at 1350°C for 20 hr, cut to shape and size with a spark cutter, and then annealed at 1100°C for 20 hr prior to use. In the KHz frequency range, the Marx composite piezoelectric oscillator was used to obtain the damping. The ultrasonic pulse technique was used to measure the ultrasonic velocities and the attenuation in the MHz frequency range. M.c.mANGALICK,-- StudentMemberAIME,formerly Research Assistant, University of Notre Dame, is now with Casting Laboratory, Chase Brass and Copper Co., Cleveland, Ohio. N. F. FIORE, Associate Member AIME, is Assistant Professor, Department of Metallurgical Engineering and Materials Science. University of Notre Dame, Notre Dame, Ind. This communication is part of a Ph.D. thesis presented by M. C. MANGALICK to the Graduate School of the University of Notre Dame. Manuscript submitted May 20. 1968. IMD Elastic Constants. Table I gives the values of the ultrasonic velocities. Values of C11, C12, and C44 calculated from these velocities are also given in Table I, and it is evident that there is very little variation in C11, C12, and C44 with nickel content. This slight variation may be attributed to inaccuracies in velocity measurements and practical differences in the orientations of the specimens. For example, in B the time interval for vl was 2.4 ± 0.05 sec giving an error in v1 of 0.235 x or 0.005 in. per sec. The elastic constants obtained by pulse technique were tested by calculating E<110>, Young&apos;s modulus for the (110) direction, from the equation: This value was compared with the value computed from the resonance bar measurements in which where fr is the resonance frequency and I, is the length of the specimen. In all cases, the values calculated from the ultrasonic velocity measurements

Jan 1, 1969

By J. G. Y. Chow, S. B. McRickard

The tensi1e properties of Ferrovac iron have been studied from 4° to 300°K. The stress required for macroscopic yielding was found to he constant below approximately 50°K. The effect of mechanical twinning on this low -temperature stress plateau was investigated. The onset of twinning occurs in this iron between 130° and 150°K and depending on its previous thermal history the twinning-stress curue may drop below or remain above the vield-stress curves as the temperature is lowered. Twinning has been shown to initiate slip in quenclzed iron at low temperatures. In no instances, however, did the onset of twinning alter the continuity of the yield stress -tempwature curve. Our data shows that carbon inhibits twinning and slip at low tem-peratures. This observation nay be used to explain the ductile-to-brittle transition in iron. The effect of fast neutron irradiation on yielding and embrittlement in iron and Fe-C alloys is offered as supporting evidence for this viewpoint. THE mode of yielding in iron at low temperatures was studied in an attempt to find an expression based on a single mechanism to describe the thermal dependence of the yield stress of iron. There are two types of inflections observed in the variation of the yield stress with temperature in iron and Fe-C alloys. The first is associated with ductile behavior and consists of a region extending 50" to 100°K above absolute zero in which the yield stress is independent of temperature. The second is observed in more brittle materials such as Fe-C alloys and irradiated iron and consists of an abrupt discontinuity in the yield curve as the temperature is lowered through a ductile-to-brittle transition point. The temperature dependence of the yield stress for iron with four grain diameters as found in this study is shown in Fig. 1. To varying degrees all the curves appear to flatten or approach an asymptotic value as the temperature is lowered below 50°K. Several other investigators1,2 have observed a plateau in the yield stress of iron and steel at low temperatures and in 1956 Louat3 presented a theory which contained an explanation for this behavior. In a subsequent exchange with Erickson and Low4&apos;5 who attributed the plateau to the onset of mechanical twinning Louat8 showed that twinning first occurs in iron and steel tested in tension at temperatures as high as 140°K which is well above the observed plateau in yield stress. Furthermore he pointed out that both twinning and slip are basically dislocation processes and that with modified parameters his original theory still applied when deformation is initiated by twinning. Variables which affect the ductile-to-brittle transition in iron are test temperature, strain rate, composition and grain size.7 LOW,8 Hahn et al.,9 and Hull10 have provided evidence which links brittle fracture at a given temperature with the specimen grain size and the onset of twinning. In fact, Hull equates the brittle fracture stress to the twinning stress. On the other hand brittle fracture has been observed in the absence of twinning and priestnerl1 has given a fracture criterion which is valid whether or not fracture is preceded by extensive twinning. The data presented here clarify the role of twinning in the low-temperature deformation of iron. Strong evidence is given that the amount and distribution of interstitial impurities such as carbon are of

Jan 1, 1965

By J. L. Martin, W. M. Campbell

A new electric logging method, called displacement logging, often gives a direct indication of the presence of mobile hydrocarbons in hydrocarbon-bearing formations. This method is based on the detection of a bank of connate water which is formed between the invading mud filtrate and virgin formation fluids in these cases. The existence of this phenomenon has beer, verified by laboratory studies and by actual field logs taken in known oil sands. INTRODUCTION During the past decade increasing use has been made of conventional electric logs to determine the amount of oil or gas in formations traversed by a borehole. This determination requires knowledge of several factors, such as true resistivity of the formation, formation factor, and water resistivity. Sometimes all of the factors necessary to make a reliable saturation calculation are not available. Also, the computations and corrections which are necessary in such a study often require the services of an experienced log analyst. It has long been the desire of exploration people to have a logging device which will locate hydrocarbon-bearing formations directly without requiring complex interpretation methods. The displacement log, while not completely fulfilling this desire, appears to be a Step in that direction. Basis for the Device The basis for this device stems from a phenomenon which occurs when mud filtrate invades a formation which contains displaceable hydrocarbons. As the mud filtrate invades the formation, most of the oil or gas is pushed out of the invaded zone, leaving residual oil. However, in addition to displacing most of the oil or gas, the connate water is also swept out, since the originally irreducible water is mobile in the presence of a water phase.1,2,3 Tonsequently, this irreducible water piles up as a bank between the virgin oil zone and the invading filtrate. If the mud filtrate is of higher resistivity than the formation water— as is commonly the case—the resulting annular zone, containing the bank of formation water, will be of lower resistivity than either the virgin oil-bearing formation resistivity or the invaded zone resistivity. This resistivity configuration, going from high to low to high again as the distance from the borehole increases, is found only in those zones which contain displaceable hydrocarbons. A device which would reliably detect this low resistivity zone would give a direct indication of mobile hydrocarbons. Illustrations This phenomenon is illustrated in Fig. 1 and 2. Fig. 1 shows a sketch of a zone containing salty connate water plus displaceable hydrocarbons, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 2 shows this zone, together with fluid content and resistivity graphs. after invasion by a fresh water mud. The resistivity pattern on moving away from the borehole is high: low: high. The absence of the low zone phenomenon in water zones is illustrated in Fig. 3 and 4. Fig. 3 shows a sketch of a zone containing salty formation water and residual oil, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 4 shows this water zone, together with fluid content and resistivity graphs, after invasion bv a fresh water mud. In this case the resistivity pattern on moving away from the borehole is high: low since there is no change in water saturation at the head ol

Jan 1, 1956

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack&apos; find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By W. H. Bassett

Beads of metal frequently appear at the ends of cast-copper wire bars and on the sides of wedge cakes near the top. These are richer in cuprous-oxide than the rest of the casting. A micrographical study of these exudations has been made. It is suggested that the material is forced through the surface while the copper is solidifying. If not eliminated in process of manufacture, it shows on the finished polished sheet copper in patches differing in color from the main body of the sheet. FIGURES 1 to 4 show the copper exudations, at different magnifications, as they appear on the ends of cast wire bars, and on the sides, usually near the top, of wedge cakes. Sometimes the exudations are in fine "drops;" at other times, large masses of the material are found. Microscopic examination of the copper exudation indicates that it is high in oxide and of eutectic proportions. Because of the difficulty of securing a suitable sample, the protuberances have not been analyzed chemically; but the spectroscope shows no indication that there are any more metallic impurities present than in the balance of the copper. The lowest copper plus silver content of the coppers studied for this? paper was 99.914 per cent.; the highest, 99.966 per cent.; so the oxygen content of the whole casting would be well under 0.07 per cent.

Jan 2, 1926

By E. T. Turkdogan, L. S. Darken, R. G. Olsson, H. A. Wriedt

Several aspects of the calcination of Michigan limestone were investigated: the rate of calcination of limestone spheres with diameters from 1.8 to 14 cm at temperatures from 800° to 1200°C by a thermogravimetric method; the temperature profile across limestone during calcination; the excess pressure developed in the interior of the stone during calcination; the pore surface area, pore volume, and effective gas diffusivity in burnt lime; and the microstructure of polished and fracture surfaces. It is found that, over a wide range of experimental conditions, the difference between the surface and center temperatures remains essentially unchanged during the latter half of calcination. From the rate of weight loss after about 50% calcination, the value 0.00126 cal per cm sec degree is found for the effective thermal conductivity of burnt lime. From the excess internal pressure measurements, i.e., 0.4 to 6 cm Hg at 800° to 1200°C, the permeability of burnt lime is estimated to be within the range 8 X 10-&apos; to 5 X 10&apos; sq cm. With increasing temperature and time of calcination, the pore structure of burnt lime coarsens as indicated by a decrease in the pore surface area, pore volume, and an increase in the average pore size. For the temperature range 600° to 835°C the ratio (effective gas diffusivity/molecular diffusivity) is about 0.18.

Jan 1, 1974

By E. M. Wise

THE properties required of gold alloys for jewelry are not well standardized, due in part to problems peculiar to certain branches of the jewelry industry, in part to the individual preference of the fabricator and to his willingness to cope with certain difficulties in manufacture, which arise with the use of certain alloys. GENERAL REQUIREMENTS In general, the properties desired may be classed as follows: 1. Color should conform to the dictates of good taste and smart style. 2. Corrosion resistance and tarnish resistance should be good. This is to a considerable extent determined by the carat. Resistance to such corrosive agents as mercuric chloride as well as certain depilatories is unreasonable to expect and difficult to meet. 3. Strength and hardness must be adequate to maintain the delicate contours of finely modeled jewelry. 4. Wear resistance must be great enough to resist abnormal wear, such as is encountered by a wedding ring in a lifetime of wear. 5. Ductility must be sufficient to permit the fabrication of drawn shells, tubes and difficult shapes. Material having a yield point of not less than 60,000 lb. per sq. in., an ultimate strength of 100,000 lb. per sq. in., and an elongation of 40 per cent. is desirable. 6. Melting point should be between 800° and 1200° C.

Jan 1, 1928