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

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 I 5 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.= 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 be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

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 I 5 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.= 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 be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By Len Ramp

CHROMITE deposits in southwestern Oregon occur along definite zones or horizons in sill-like ultramafic intrusions. These horizons are here referred to as ore zones and are distinguishable only by relatively Shin and scattered, discontinuous chromite occurrences. The zones are tabular in shape but are usually folded and faulted by the intensive post-intrusion deformation the ultramafic rocks have undergone. A single zone may contain disseminated, nodular, banded, or pods of massive chromite. The typical chromite deposit is composed of a series of thin lens-shaped bodies that lie along a definite plane and generally show evidence of magmatic flow with their long dimensions aligned in the direction of flow. A body of chromite often pinches down to a narrow wisp only a fraction of an inch thick. This thin streak of chromite may point to or be connected with another body of chromite. In some deposits the orebodies have a definite rake. The depth at which chromite may be found can be predicted by its position in a folded intrusive, provided that adequate structural evidence is available. Although the ore shoots are characteristically discontinuous, there is theoretically no limit to the depth at which chromite may be found. Origin: All the chromite deposits examined in southwestern Oregon are of magmatic origin, that is, the chromite was an original constituent of the peridotite magma and became segregated in varying degree from the magma to form the ore de- posits. Examples of early, intermediate, and late magmatic chromite have been recognized in the area. Crystallization of the principal minerals (olivine, pyroxene, and chromite) was apparently near completion at the time of intrusion of the peridotite magma. The magma acted as a viscous crystal mush stringing out aggregates of pyroxene and chromite in the direction of flow. These streaky accumulations are termed schlieren.

Jan 8, 1957

By Hsun Hu, R. S. Cline

The annealing behavior and the mechanism of re-orientation during recrystallization of iodide titanium cold-rolled 94 pct have been studied in detail. Results indicate that recrystallization occurs by the nucleation and growth of new grains, as in other common metals. Recrystallization nuclei form by the coalescence of subgraim, and the change in texture as a result of recrystallization is largely due to selective growth among the nuclei formed. The annealing of titanium is characterized by a wide range of overlap of the various stages of the annealing process, which may be responsible for a range of activation energies observed, and for the apparently gradual change in the annealing texture as a function of time or temperature. The deformation and recrystallization characteristics of titanium and zirconium are very similar. In cold-rolled strip, the deformation texture consists of two symmetrically oriented components, each having the basal plane laterally tilted at about 30 deg from the rolling plane and the [1010] direction parallel to the rolling direction. Upon annealing for recrystallization, the change in texture can be described, for simplicity,* as rotations around [0001].2'6'8 According to McGeary and Lustman,' recrystallization occurs in zirconium through normal growth of the subgrains, which they called "domains", without the nucleation of new grains; and the magnitude of rotation around the [0001] axis increases gradually during the progress of recrystallization. If these conclusions were true, the mechanism of recrystallization in zirconium would be basically different from that in most metals, since it is commonly known that recrystallization with reori-entation always involves the migration of high-angle boundaries. In an attempt to clarify the situation, the mechanism of reorientation during recrystallization in iodide titanium cold-rolled 94 pct was studied in detail. The structural and textural changes upon annealing at various temperatures were examined by optical and transmission-electron microscopy, X-ray pole figures, pole density distribution measurements, and micro-beam techniques. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. An iodide titanium crystal bar was are-melted and solidified in a cold-hearth crucible under a purified argon atmosphere. The solidified ingot had dimensions of approximately 3 by 1/2 by 3 in. One face of the ingot was somewhat uneven, but was as clean and shiny as the remaining parts of the ingot. Large grains with a Widmanstatten internal structure were clearly shown on the shiny surfaces, indicating the occurrence of P — a transformation upon rapid cooling from the melt. Analysis of the are-melted ingot indicated C 0.033, N 0.010, H 0.013, 0 0.002 in weight percent, and traces of iron, copper, and silicon as detectable impurities. The ingot was cold-rolled -40 pct to 0.300 in. thick with a reduction of 0.005 in. per pass. The defects on the uneven side of the ingot were then removed by machining. This reduced the thickness to 0.285 in. The piece was then recrystallized by annealing at 800°C for 1 hr in a fused silica boat charged into a fused silica tube furnace under a vacuum of 10~5 mm Hg. To refine the grain size, the recrystallized metal was again cold-rolled 40 pct to 0.170 in., then annealed at 700°C for 1 hr. These treatments yielded a strip with a uniform equiaxed grain structure, having a penultimate average grain diameter of 0.04 mm and a hardness of approximately 90 Dph. Final rolling reduced the thickness from 0.170 to 0.010 in., corresponding to a reduction of 94 pct. The strip was rolled in both directions by reversing end for end between passes. Surface lubrication was provided by oil-soaked pads attached to both rolls. Specimens of 1 in. length (for X-ray examinations) and +in. length (for hardness and microstructure examinations) were cut from the rolled strip, and a width of & in. was cut from the edges of each specimen by a jeweler's saw. These specimens were then etched in a solution of 10 cu cm HN03, 5 cu cm HF, and 50 cu cm H,O to 0.008 in. thick to remove the surface metal, as well as the distorted metal at the saw cuts, prior to annealing or measurements. To minimize any surface reaction with the atmosphere, all specimens were kept in an evacuated desiccator. Isothermal Anneals. All annealing treatments were conducted in vacuum in a fused silica tube furnace as described earlier. The temperature of the furnace was controlled to within *2"C. The specimen was placed in a fused silica boat, then pushed into the hot zone of the furnace. It took about 5 to 6 min for the specimen to reach the furnace temperature. After the specimen was held at temperature for a desired length of time the boat was pulled to the cold zone of the furnace; the heating-up period was excluded from the isothermal annealing time. Thus, the uncertainty in annealing time is higher for very short anneals, but negligible for long anneals.

Jan 1, 1969

By Zay Jeffries

AN acute current shortage of copper, with the prospect that conditions may become worse, indicated by Office of Production Management information. Present estimates of copper requirement for defense indicate that nearly all the available metal will be required in the future for this purpose. Severe dislocations are, expected, but the objective is to distribute the copper available for civilian use in such a manner as to minimize these dislocations. The advisory committee on metals and minerals has been asked for a suggestions which may be helpful in meeting this situation.\

Jan 1, 1941

W. N. Triplett (Geology of the Silver-Lead-Zinc Deposits of the Avalos-Providencia District of Mexico, P. 583) was born in Tecumseh, Mich., and attended the University of Michigan and Massachusetts Institute of Technology. From 1912 to 1917 he worked for Moctezuma Copper Co., a Phelps Dodge subsidiary at Nacozari, Sonora, Mex. He served in Army as Second Lieutenant Field Artillery from 1917 to 1918 and from 1919 to 1922 returned to Moctezuma Copper Co. From 1922 to 1952 he has been with Compania Minera de Penoles, S. A., a subsidiary of American Metal Co., Monterrey, N. L., Mexico in Unit Dept. as chief geologist and at present is consulting geologist. Mining geology and operation is of particular interest to Mr. Triplett. He presented a previous paper before with M. W. Hayward entitled, "Occurrence of Lead-Zinc Ores in Dolomitic Limestones in Northern Mexico." Besides being an AIME member, he holds membership in Society of Economic Geologists. Fishing, hunting and photography are his favorite hobbies.

Jan 1, 1952

By L. C. McCabe

THE object of the present investigation was to discover a physical basis for rank differentiation of coals, particularly the coals of the Illinois basin. Vitrain1 was selected as the most appropriate coal material to use in the investigation, because of its homogeneity and ease of acquisition and handling. Previous Investigations.-Hoffman and Jenker2 have shown that their index of reflection is a characteristic of coal rank and that the Leitz slit microphotometer may he used in determining the different intensities of reflection. Zhemchuzhnikov3 measured the luster of several Russian coals with a color analyzer and found that the degree of luster was indic-ative of rank. Luster-volatile matter curves based on data from Sucan and Donetz coals were satisfactorily used for determining the rank or volatile content of other coals after the luster strength was determined. In 1934 Fisher4 reported refractive indices of 1.76 for bituminous vitrain and 1.87 for semibituminous vitrain. Investigation of Angle of Polarization.-Early in the present investiga-tion several determinations of the refractive indices of the vitrains were made by immersing the minus 150 plus 200-mesh powder in oils. It was found that all the samples fell within the range 1.6 to 1.8. However, difficulty was encountered in securing oils in this high index range that were closely enough spaced to separate some of the coals. The writers made a number of determinations of the angle of maxi-mum polarization from the polished surfaces of the vitrains and derived their refractive indices by the procedure described in the follow-ing paragraphs.

Jan 1, 1937

By Morris A. Steinberg

Because of the broad scope of my topic I will discuss my subject from the point of view of a present status of the metallic materials that are used in structures and will dwell primarily on those structures related to high- performance aerospace systems. Thus, I can best portray the status of these structural materials as related to existing transportation systems, delineating some of the highlights of alloy development, fabrication, and properties obtained. I shall point out what are, in my opinion, the needed solutions to pressing unsolved metallurgical problems connected with certain selected metals: aluminum alloys, beryllium, titanium, steels, superalloys, refractory metals and some metal-matrix composites. Aluminum Alloys For a number of years a series of strong aluminum alloys used for airframes has had an important bearing on the development of minimum- weight, highly efficient structures. Among these alloys are such familiar ones as 2024-T3, 2014-T6, 7075-T6, 7079-T6 and 7178-T6. A review of the development and use of strong aluminum alloys in aircraft structures indicates that before about 25 years ago there was very little application of products other than forgings in the high-strength tempers produced by precipitation heat treating to T6- or T8-type tempers. 1 As stated by Dix in 1944, "There has been a gradual evolution in engineering viewpoint regarding the mechanical characteristics which are required in a structural material suitable for aircraft. Formerly, emphasis was placed on a generous spread between yield and tensile strengths, on elongation, on impact strength and on resistance to corrosion. Aircraft structural engineers still differ widely as to the importance which they attach to these proper tie.” 2 It is fair to say that this evolution is still taking place, that the problem is much the same in 1970 as in 1944 - except that strength levels have advanced some - and the question remains as to how far we can go in that direction. In the meantime, a new group of alloys has received acceptance and widespread use. The first alloy of this group, 7075-T6, was formally introduced by Dix's 1944 paper. The drastic changes that have taken place in the size and configuration of components employed in air-

Jan 1, 1971

By R. W. Borio, T. S. Spicer

Inflammability and crossing point apparatus were used to study the influence of increasing amounts oi such inerts as ash, fly-ash, pyrite, limestone and Portland cement with several pulverized bituminous coals. The results indicate that it requires large proportions of inerts to substantially suppress the ease of ignition. The ignition phase of the combustion of solid fuels has been under study periodically since 1900. With the advent of pulverized coal firing some 60 years ago, a technique now dominating the coal utilization field, the ignitibility characteristics have become increasingly important. Much of the early work was directed toward the prevention of coal dust explosions and improved mine safety rather than combustion. Many factors affecting ignitibility have been studied and numerous methods devised in an effort to measure the ignition temperature and these have been reviewed by other authors. A recent survey was made by Finney and Spicerl in 1959, so a discussion of previous work will be omitted. Despite these efforts, the initial stage of combustion, termed ignitibility, is still a little understood phenomenon. In fact, no ASTM method has been adopted for the calibration of this illusive property. However, a D-5 Subcommittee XVI on Ignitibility of Coal and Coke of ASTM (now inactive) defined ignitibility:' "The ignitibility of a fuel is that char-

Jan 1, 1963

By J. Weertman

It is shown that conditions suitable for the conversion of straight dislocations into helices are common in crystals hardened either through long-range dislocation interaction or by jog formation on dislocation lines. For dislocations other than screw dislocations or dislocations nearly screw in orientation, helices can be formed with the aid of core difhsion at temperatures low relative to the melting point of the material. It is assumed that, once formed, helices will degenerate into dislocation tangles. THE dislocation tangle is one major dislocation arrangement observed by the transmission electron microscope which had not been predicted previously from dislocation theory. Since first being observed, the tangle itself has become important in applied dislocation theory. The Cambridge school (P. Hirsch) bases part of its theory of work hardening upon this phenomenon.' In spite of the fact that the tangle obviously is a structure of prime importance to a cold-worked crystal, until recently relatively little attention has been paid to the question of exactly why or how tangles arise. It was generally assumed at first that cross slip and perhaps jog formation will lead to tangles. However Wilsdorf and schmitz2 concluded that cross slip cannot markedly contribute to the tangles. The Wilsdorfs and Maddin3'* have proposed that tangles arise by means of prismatic dislocation loops and superjogs which are produced by a precipitation of point defects. Dislocations with superjogs or which have joined with prismatic loops are themselves dislocation sources and they can produce new dislocations, a process they call "mushrooming", which then tangle with each other. There is no question that the Wilsdorfs et al. mechanism as well as the cross slip one can pro- duce tangles. However these may not be the only paths leading to tangle formation. In this paper we wish to consider another way tangles can form. Our work will be based on the theory of dislocation screw We wish to show that whenever a crystal is cold-worked there always is present a "driving force" leading to helix formation and thus to tangle formation. We do not expect to observe well-developed, regular helices in cold-worked metals. Rather we would expect that after a helix is formed random interactions with nearby dislocations will cause a well-developed helical dislocation to go over into an irregular form. A dislocation tangle is, of course, a grouping of dislocations with irregular forms. Therefore we feel that, in accounting for the formation of dislocation tangles, it is sufficient to show that many dislocations in a cold-worked crystal will take on helical form. The crucial step is helix formation. In order to have a straight dislocation assume a helical form, diffusion of vacancies, or interstitials, must occur. Our discussion of tangle formation therefore will be limited to crystals which have been deformed at temperatures ranging from about one fifth to half their absolute melting point. In this tem per a ture range appreciable core diffusion is possible. (There is no problem in explaining tangle formation at temperatures greater than half the melting point. At such temperatures dislocation climb through a bulk diffusion of point defects gives an extra degree of freedom to dislocation motion. This extra freedom of motion makes tangle formation easy.) At temperatures much below one fifth the absolute melting temperature diffusion processes are sufficiently slow that helix formation does not occur. Of course helix or tangle formation could occur in material deformed at very low tempera-tures which was subsequently warmed in order to make the thin specimen necessary for electron-microscope examination. Since within the temperature range of approximately one fifth to half the melting temperature the diffusion of point defects in the core of the dislocation is rapid, we can reasonably assume that within

Jan 1, 1963

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By C. T. Malcomson

An elaborate series of experiments has been conducted during the past three years at Irvington, N. J., which has resulted in the perfection of a process for the manufacture of smokeless fuel from high-volatile coals, and for the recovery and refinement of the coal-tar products derived therefrom. These experiments have been financed by Messrs. Blair & Co., of New York, and were conducted under the direction of Charles H. Smith, a member of this Institute, and the inventor of the process. The low-temperature distillation of coal has interested investigators for many years. Sporadic attempts have been made to solve the mechanical problems, but until the Smith process was developed, they were not carried to conclusions of economic value. The present coal shortage and the increasing demand for smokeless fuels make this subject one of timely interest. DescRiption of Plant The following equipment was installed and operated during the experimental period: Four horizontal and two vertical units of commercial size for the low-temperature distillation of the coal; two vertical, two horizontal, and two inclined benches for distillation of the briquets at medium and higher temperatures; presses and auxiliary equipment necessary for making briquets; and a complete byproduct recovery and tar-refining plant. This commercial equipment is provided with gas and electric meters, pyrometers and other apparatus for recording accurately the results of all experiments. There is, in addition to the commercial equipment, a complete chemical laboratory with distillation and recovery apparatus, including facilities far refining and cracking the tar and measuring the yields and calorific value of the gas. This apparatus makes possible a study on a small scale, of the various problems involved in the process. Description of Process Mr. Smith's experiments have resulted in the production on a commercial scale of: 1. A fuel, called Carbocoal, which, for convenience in handling, is prepared in briquet form.

Jan 1, 1920

By R. G. O’Meara, M. M. Fine

ONE of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite.[t] In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.1 The outlook for the postwar market for fluorite is encouraging. Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status.3 ACKNOWLEDGMENT This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. O. E. Anderson, mill superintendent,

Jan 1, 1946

By John M. Logan, John Handin

Quasi-dynamic triaxial compression tests have been done for the first time at confining pressures to 7 kb. The intermediate strain-rate apparatus employs a gas loading cylinder which allows axial strain rates up to 102/sec on a sample 2 cm in diameter and 4 cm long. Samples can be deformed at confining pressures to 7 kb. Strain gages bonded to the loading piston and to the jacketed specimen allow internal measurements of load and sample strains respectively. Westerly granite has been deformed at confining pressures to 7 kb, room temperature, and axial strain rates of 10-2 to 1/sec. An increase of ultimate strength with confining pressure was found as expected. The ultimate strength was also found to vary directly with increasing strain rate; the rate of rise increases with confining pressure. Brittle deformation has dominated the sample behavior. Solenhofen limestone has been deformed at confining pressures to 3 kb, room temperature, and axial strain rates of 10- to 10/sec. The brittle-ductile transition was found to take place at about 1.5 kb confining pressure at a strain rate of 10/sec.

Jan 1, 1971

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By P. S. Kotval

THE nominal composition of "hconel" alloy 718 is 53 pct Ni-19 pct Cr-19 pct Fe-3 pct Mo-5 pct Cb-0.8 pct Ti-0.6 pct A1-0.05 pct C. The nature of the fine strengthening phase in this alloy has been open to debate. iseelstein' has identified the strengthening phase in the matrix of "Inconel" alloy 718 as a colum-bium-rich fcc y' precipitate. Wagner and Hall2 have noted that the metastable y' precipitate overages to an orthorhombic Ni3Cb precipitate which manifests itself as an acicular phase. These authors thus clarify Kaufman and Palty's earlier suggestion3 that the strengthening phase is orthorhombic NisCb. Wagner and Hall's review also reports work by cometto4 which suggests that the fine strengthening phase is not fcc / but bct with a Ni3V type structure and based on the Ni3Cb composition. Kir man and warringtons have shown by analysis of electron diffraction patterns that the metastable strengthening phase in a 55 pct Ni-15 pct 0-25 pct Fe-5 pct Cb alloy is bct and based on the Ni3Cb composition. Raymond~ has provided electron diffraction evidence which indicates that "y'" in "Inconel" alloy 718 is bct in structure. This note presents unambiguous data on the structure of the strengthening phase in "Inconel" alloy 718* ihe samples of this alloy were provided by courtesy of the ASTM task group on phase identification in 'superalloys. after prolonged aging. The electron diffraction patterns presented show that strengthening phase is not y' but bct as was proposed by cometto,' supported by Raymond,~ and identified by Kirman and warringtons in a similar system. Fig. 1 shows a selected-area diffraction pattern taken from a thin foil of "Inconel" alloy 718. The sample had received a final aging treatment of 1118 hr at 1200°F to precipitate the strengthening phase in the matrix. Fig. 2 is a schematic representation of the features in the diffraction pattern. The matrix orientation is (0i2)~,, as is shown by the indexed zone in Fig. 3. Figs. 4, 5, and 6 illustrate that the pattern, Fig. 1, is composed of three bct zones, viz., (0i4), (2i0), and (i01), respectively. These three zones correspond, respectively, to the alignment of the c axis of the bct unit cell with the [001], [loo], and [OlO] directions of the fcc matrix and serve to illustrate the fully coherent relationship of the precipitate structure with the matrix. The streaking of certain reflections is also consistent with the above orientation relationship. The interpretation of the diffraction effects presented here shows the metastable strengthening precipitate in "Inconel" 718 alloy to be bct in structure and demonstrates that it is not an ordered fcc y' phase.

Jan 1, 1969

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By A. B. Parsons

DOWN in Washington an army of individuals constituting the government of a so-called "'democratic" nation is trying to manage the conduct, in its rnultifold phases, of the greatest war in history for the country that is potentially, at least, the strongest in the world and on which, consequently, the major responsibility rests. The enterprise is one of unprecedented magnitude and complexity. That individuals and groups have made and are making serious blunders, both as to the establishment and execution of policy, is to be expected.

Jan 1, 1942

By Yap Chu-Phay

ALTHOUGH chronologically, the Sb-Bi system was the first one studied by the writer, the theoretical basis of the equations used in this paper is fully discussed in the writer's paper on the iron-carbon system,1 because he believed that many would be more interested in the iron-carbon alloys. He suggests, therefore, that the reader consult that paper to familiarize himself with the theoretical aspect of the thermodynamic treatment outlined herein. This paper is divided into two parts: Part I deals with the Sb-Bi system and Part II deals with the lead-rich side of the Sb-Pb system. Although the former system has not much practical interest now, it has great theoretical interest in that it, is the one system that for a long time was thought to have (and under specific conditions still has) an anomalous solidus, which no amount of physical investigation could adequately account -for. The latter system of course, is particularly interesting in the lead-rich end. It will be shown that the thermodynamic method is capable of predicting reliably the equilibrium position of the solidus, and thus acts as a check on the experimentally derived solidus.

Jan 1, 1931