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By D. Cubicciotti

IT has long been known that some metals are capable of being dispersed or dissolved in certain of their fused salts.' Davy' and Bunsen³ were among the first to observe that in some fused salt electrolyses, a highly colored, strongly reducing salt phase appeared in the neighborhood of the cathode. Later workers found that the current efficiency of the electrolysis was markedly reduced when such a phase appeared. It was also found that the strongly reducing salt could be made by melting the metal and normal salt together. Chemical analysis showed that in such salts the metal ion to anion ratio was always larger than in the normal salt. From such observations arose two different explanations of the nature of metal in salt solutions. When a solution of this type is quenched, it is possible to find small globules of metal in the salt. From this and other observations, Lorenz' and co-workers assumed the metal in salt solution to be a colloidal dispersion of metal in the fused salt and called it "metallnebel" or metal fog formation. They made a number of experiments to substantiate this point of view. Another school felt that when the metal dissolved it reduced the salt partially to a mixture or solution of normal salt and subsalt. Both of these ideas could explain the strong reducing character of the salt formed and the low current efficiency of the electrolysis. If either a metal colloid or a subsalt were formed at the cathode and diffused to the anode, it would be oxidized to the normal salt. Thus a cyclic process of oxidation and reduction could be set up conducting the current without giving rise to a net change in the system. These facts led the author to investigate some of the properties of metal in salt solutions with the hope of elucidating their nature further. Among the metal-salt systems that form metal in salt solutions most markedly are the alkaline earth metal-halide systems and cerium, bismuth, and cadmium halides. Other systems of halides, oxides and sulphides form such solutions to a lesser degree. The first work undertaken was a study of the temperature-composition diagrams of some of the systems." From such diagrams it would be possible to distinguish between a subhalide formation or a colloid. A subhalide should give rise to characteristic changes in the phase diagram, while a colloidal dispersion of metal in salt would not alter the freezing point of the salt. The results obtained on a number of alkaline earth metal-halide systems were all quite similar. Fig. 1 shows the barium-barium chloride system. The other

Jan 1, 1954

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

IT was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a. component of the pulp, of a mass solubility of the general order of a fraction of a milligram to 15 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.2 The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. EXPERIMENTAL Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well beyond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipita-

Jan 1, 1943

By John Chipman, Eric R. Jette, O. B. Ellis

IN the study of the chemical reactions occurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Herty1 and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schackmann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete analyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were remelted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abandoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the constituents of basic open-hearth slag. EXPERIMENTAL HEATS The first set of measurements on slagmetal equilibrium was made in the Research Laboratories of the American Rolling Mill Co. at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Research Laboratories at Massachusetts Institute of Technology, and will be referred to as series B. Series A.-The induction furnace used has been described.5 Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

By P. Farrar, H. Margolin

The Ti-Pb diagram was investigated in the region 0 to 58 pct Pb and from 500°C to liquidus temperatures. Three reactions were encountered: I—ß?a+Ti Pb at 725 10°C; 2—ß+L?Ti4Pb at 1305+ 10°C; and 3—the possible eutectic L-+Ti,Pb and y between 1200" and 1300°C. LEAD-RICH alloys have been investigated by Nowotny and Pesl,' who used sintered compacts and studied the region from 37.5 to 100 pct Pb by X-ray diffraction analysis. The only phase found in addition to titanium and lead was the hexagonal compound Ti Pb. Alloy systems of lead with metals of the transition group, such as iron, chromium, tungsten, cobalt, nickel, or manganese, generally show little liquid or solid solubility.' Craighead et al.,3 however, indicated that lead is soluble in a and ß titanium to at least 2.1 pct. They also found that approximately 50 pct of the lead added was lost during the arc-melting of Ti-Pb alloys. In the present investigation, are-melting also was used to prepare Ti-Pb alloys and similarly large lead losses were encountered. Experimental Procedure Alloy Preparation: Considerable difficulty was encountered in the melting of the Ti-Pb alloys and a number of experiments were performed before the method described was developed. Alternate layers of lead and titanium were wrapped with titanium sheet and compacted. This "sandwich" was annealed at 300" to 350 °C and was melted according to the procedure described by Cadoff and Nielsen.' Using a low current, 150 amp, and an argon atmosphere, four to eight 10 to 20 sec melts were made on each alloy, with the button being turned over between each melt to insure homogeneity. In the high lead range, the preliminary sintering was found to be of doubtful value and was eliminated. In the region above the nominal composition of 70 wt pct Pb, the alloys prepared in this manner always consolidated into two phases. The outside appeared to be composed entirely of lead and the inside was a Ti-Pb alloy. In order to determine whether this phenomenon was caused by a miscibility gap, master alloys with a nominal composition of 40 wt pct Pb were machined and mixed with various percentages of lead sheet. This mixture was compacted and melted in the same manner as the other alloys. Although these alloys were not homogeneous, they did not show the layering that was observed

Jan 1, 1956

By R. J. P. Lyon

It is usually assumed1,2 that ore deposition is relatively slow, taking place over tens of thousands of years. Yet many syntheses and phase changes can be completed in the laboratory in a matter of hours, under essentially the same pressure and temperature conditions to be expected in nature. Much has been written about geothermometry, and Ingerson's recent summary2 an hardly be surpassed. Rather than review the whole field, this article will deal specifically with diffusion rates in solid solutions* of the sulfide minerals. In the study and application of temperature-indicating phenomena to problems of ore genesis, the time factor has often been neglected. In the particular case of sulfide systems, the speed of unmixing and diffusion of the constituent phases in the solid solutions has seldom been considered when laboratory data are applied to the genesis of natural sulfide ores. Chalcopyrite and Bornite Intergrowths: Chal-copyrite and bornite are copper iron sulfides often found in association. In many ores the individual grains appear to have mutual boundaries, but bladed intergrowths are quite common. Early workers in the field, " deduced that while these patterns could have been formed by replacement, they could be experimentally reproduced from the unmixing of solid solutions of the two previously homogenized at 475°C. Much of the ore from Roan Antelope mine in the Rhodesian Copper Belt exhibits these bornite-chalcopyrite intergrowths, from which it has been deduced that the ores could have been subjected to a minimum temperature of 475°C. In several recent interpretations,' this temperature rise has been considered to result from a regional metamorphism of an original syngenetic copper-bearing sediment. The same temperature rise to 475 °C was suggested from similar intergrowths in the sulfide- • The general subject of solid solution in structurally similar minerels is treated in many texts'. :' ' and will not be further elucidated. bearing ore from the Happy Jack uranium mine8 on tile Colorado Plateau, although this temperature had a different origin. In 1931 SchwartzV etermined that 475°C represented the unmixing temperature of his bornite-chalcopyrite solid solutions but, more important, that the characteristic intergrowths of bornite and chalcopyrite could be preserved only if the solid solution were chilled quickly to room temperature. This significant corollary has been almost completely neglected by both Davis and Miller.7,8 By suitably decreasing the cooling rate, Schwartz found that the original pattern of the intergrowth was reformed (Fig. 1). The cooling rate was critical. In cooling from 475°C to room temperature in

Jan 1, 1960

By C. M. Young

Wherever salt is extracted from the ground as an artificial brine produced by pumping down fresh water to dissolve the salt, subsidence of the overburden is a possibility, though apparently few cases of such subsidence have been noted and detailed records are wanting. This description is intended as a record of subsidence that may permit the forcasting of similar occurrences in other cases; the data were supplied largely by R. B. Lee, city engineer of Hutchinson, Kans. About eleven years ago, ground movement occurred at a neighboring salt plant, when the surface assumed the form of a shallow funnel. Movement was probably due to a flow of sand into a well through a poor seal or a broken casing. The salt deposit increases in thickness from the east until at Hutchinson, where the subsidence occurred, it is about 310 ft. thick. The interbedded layers of shale vary in thickness from mere traces to about 7 ft. While knowledge of the shale content of the beds is not exact, the log of a shaft 3 miles east of Hutchinson indicates that shale forms about 25 per cent. of the total thickness. This shaft does not reach the bottom of the salt by about 60 ft., but there is no reason to think that the lower part of the bed is different from the upper. Logs of wells sunk to the bottom are not sufficiently detailed to be of much value. Above the salt is the shale of the well-known Red Beds. The thickness of this is variable, principally because of its eroded surface, but at the mine it is 340 ft. This shale is variable in character and strength, but contains no strong members of limestone or sandstone. If the support is removed, very probably it will subside. The Arkansas River flows across the salt district and Hutchinson is situated on the flood plain. Between the top soil, which is about 8 ft. thick, and the shale is 60 to 100 ft. of water-bearing sand and gravel. The process of removing salt, at least in the case of the earlier wells with which we are concerned, is as follows: An 8-in. hole is put down through the sand and gravel by means of a drive pipe, which is bedded in the shale. Prom the top of the shale, a 6411. hole is drilled through the shale, to, or nearly to, the bottom of the salt. Casing is put in to a depth of about 140 ft. to shut off a water-bearing layer in the shale.

Jan 1, 1927

By ROBERT R. ABUOTT

Discussion of the paper of Prof. Albert Sauveur and, G. A. Reinhardt, presented at the Cleveland meeting, October, 1912, and printed in Bulletin No. 71, November, 1912, pp. 1335 to 1341. ROBERT R. ABBOTT, Cleveland, Ohio :-The possibilities of the commercial application of the facts brought out in this paper have been the subject of many experiments by me during the past four years. It will be well to call attention to several facts having a commercial bearing upon the problem: (1) The lower critical temperature (Ac) of a 3.5 per cent. nickel-steel of low carbon (say 0.20 per cent.) content is about 710° C. This is not lowered to any extent by increasing its carbon content by carbonizing,. By this I mean that a steel with Act occurring at 710°, must, after carbonizing, be heated above this temperature before quenching in order to make it hard. This is not contrary to Guillet's diagram, although at first thought it may seem so, due to a confusion of the Act and the Ar1, points. His diagram merely gives the physical condition of the steel upon slow cooling. Now a steel of 1.20 per cent. of carbon and 3 per cent. of nickel (point " B " of the diagram) may be martensitic upon slow cooling from three causes: (a) Its Ar1 point is below the normal atmospheric temperatures. (b) The time element is so important that the change from martensite to pearlite and cementite does not have time to occur even with this slower rate of cooling. We of course know that nickel has the tendency of retarding this change. (c) A combination of the above two causes. (2) With increasing nickel content the ability of steel to absorb carbon decreases. (3) Many carbonized nickel-steels show a martensitic. structure upon air-cooling, and yet ire so soft that they are of no commercial value.

Dec 1, 1912

By Virgil Miller, F. B. Petermann, S. F. Ravitz

The Cle Elum nickeliferous iron deposit is in Kittitas County, Washington, in a rugged, mountainous region about 23 miles north of the town of Cle Elum. The Biewett Pass deposit, which is similar in character and occurrence, is in Chelan County, about 18 miles east of the Cle Elum deposit. A more or less continuous ore zone may extend between the two deposits, since iron ore is reported to have been discovered at Iron Mountain, which lies directly between them. The ore probably was formed by meta-morphism of laterite resulting from Ieach-ing of serpentine derived from peridotite. It consists largely of magnetite grains distributed through a matrix of limonitic material containing a small amount of hematite and chromite. Many of the chromite grains have shells and inclusions of magnetite. The magnetite grains range in size from 1200-mesh to 1/4-in., the average size being 48 to 65-mesh; the chromite grains range from 20 to 150-mesh. The gangue minerals are olivine and serpentine with a small, amount of chlorite, and appear both as very thin bands in the ore and 's minute fragments in the limonitic matrix. The nickel is present as minUte inclusions of a nickel silicate mineral within the magnetite and gangue par- ticles, varying in size from 1500 to about 280-mesh. Detailed analyses of 3000-lb. lots of Cle Elum and Blewett Pass ore are given in Table I. TABLE i.—Analyses of Ore Samples Per Cent Ore from Constituent cle Elum' Blewett Pass Cr....................... 2.23 2-12 Ni...................... 1.43 0.9s Fe...................... 52.9 41.4 SiOz.................... 5.6 13.4 CaO.................... 0.3 0.8 MgO................... 4-1 7-5 AI2O3................... 7.0 2.g P...................... 0.022 0.034 S....................... O.O1 o.oa Mn..................... I.I 0.4 Ba..................... nil co..................... o.oa 0.02 CU..................... 0.02 0.03 As...................... 0.03 Au..................... nil Ag°..................... O.58 Pt...................... ml Fe++.................... 8.9 5-9 Fe+++.................. 44-0 35-5 « Ounces per ton, 1 sr,cte,so,","&&$ally absent: B, W, M~, T~, V, ~i, Bi, Pb. Sb. Sn. Be, In, Hg. Zn, Zr. Cd. Preliminary Tests Attempts to beneficiate the ore by ore-dressing methods, including various 'cornbinations of sink and float, tabling, jigging, flotation, and magnetic separation, were consistently unsuccessful. A wide variety of roasting and leaching tests were made on both raw and reduced ore, but in most of the tests little or no nickel was extracted, and in none did the extraction exceed 50 Per cent. No nickel could be volatilized as the carbonyl. by treating reduced ore with carbon monoxide. Fairly good sepa-

Jan 1, 1944

QUICKSILVER is a body that consists of flowing and liquid materials, almost like water with a shining whiteness; it is composed by Nature of a viscous, subtle substance with an overflowing abundance of moistness and coldness together. This composition, in the opinion of the philosophic alchemists, is a thing that is very disposed to become metal-indeed they say that it is the original seed of all metals. When it lacks the warmness and dryness or the specific time that they require, it cannot congeal and so remains in the form that we see as an imperfect thing without becoming metal. These clever investigators have also called it mercury in consideration of its properties, perhaps because of its resemblance to the planet of him whose actions place him between gods and men, according to the poets in their stories. Thus these investigators think that this has a similar place among perfect metals, since it is the primary mineral matter. It might also be that they called it so because like the god Mercury it is winged and fugitive, and by virtue of its powerful subtlety penetrates all things and can issue forth from them at will. But let it be called by any name they wish-it does not matter to us. I, like them, shall sometimes call it mercury and sometimes [23 ] quicksilver as it has been named to me, and you will understand it as such. Now I shall leave aside the disputes on whether it is the primary matter of metals or not, since I have said enough concerning this question in the first chapter of the First Book. In order to approach what the philosophers say about it, I say that it may well be material about to be converted into metal, but since it is seen to be so ill-proportioned and so badly decocted, I cannot believe that it can be disposed to the generation of all kinds of metals. Indeed, if it is, I think that if its necessary processes had not been interrupted it would be more apt to generate lead, tin, iron, or even silver rather than copper or gold. And if we wish to consider it in relation to the natural complexions [of metals] or to the power of the, planets, I think that mercury is far distant from those of gold and from the power of the sun and of the moon. Therefore I say that if it is not what I have said, it is a thing that Nature has been pleased to make as it is. I am led to say this because all of it that I have seen has had the same

Jan 1, 1942

By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943

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Jan 1, 1940

By Henry Louis

Four alloys of gold and silver were prepared, containing the metals in the following proportions by weight: I. Gold:Silver::1:2.62.

Jan 1, 1894

James W. Neill, Salt Lake City, Utah: Mr. Keller observes, in his interesting paper, that his copper mattes show a constant tenor of 21 to 23 per cent. sulphur; and continues," Many of these analy-

Jan 1, 1894

PROF. COURTENAY DE KALB, Kingstou, Oat. (communication to the Secretary): It. may be due to some lack of carefulness in expression that Mr. Upham seems to imply that there

Jan 1, 1899

Jan 1, 1951