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By R. T. DeHoff

A theoretical development is presented which reformulates Fick's first law for diffusion in the solid state. The diffusion flux of component i in a multi-component system, Ji, is related to its local concentration, ci, and local jump frequency, ri : where a is a geometric factor and d is the jump distance. The product, ciri , is defined as the local concentration of atomic jumps for component i. The analog to Fick's second law is also derived. A solution to this equation is presented, which permits the experimental determination of the variation of atom jump frequency with composition in multicomponent systems. HISTORICALLY, the description of diffusion in the solid state has been presumed to be best approached as an application of more general diffusion laws, known as the phenomenological equations. These equations relate the flux, Ji, of the various components, expressed in atoms, grams, or volume, to the driving force involved, expressed as either a compositional or chemical potential gradient, sumption that the flux is simply proportional to the driving force is the foundation of this approach. The phenomenological equations take the form: where the concentration gradients are assumed to be the driving force, and: if the chemical potential gradient is taken as the driving force. The coefficients Dij in Eq. [1.] are the "diffusion coefficients"; the elements of the corresponding matrix in Eq. [2], the Mij, are called the "mobilities". Eqs. [I] and [2] may be considered to be definitions of these phenomenological coefficients. A formidable body of literature has been generated about these equations; this literature dates back to their original formulation for the simplest case of binary diffusion in a fluid, by Adolf Fick, in 1855.' This description has been shown to be self-consistent. However, the "constants of proportionality", the Dij or ,Mij, are not constant: they vary with composition in all but the simplest systems. Even in the case of tracer diffusion, wherein it can be shown that the diffusion coefficient is constant, the mobility, which is considered in irreversible thermodynamics to be the more physically meaningful quantity, varies with the concentration of the tracer involved.' In more complex systems, it is necessary to evaluate the entire matrix of phenomenological coefficients, as a function of composition, in order to describe diffusion locally. Further, in order to determine this matrix experimentally, it is necessary to produce diffusion couples that have different sequences of compositions; the matrix may be evaluated only at points where these "composition paths" cross.* Finally, and perhaps most

Jan 1, 1969

By Edward W. Parker

At the Seventy-sixth meeting of the Institute, held in New York, N. Y., February, 1899,I presented a paper on this subject entitled, Coal-Cutting Machinery,' which has become somewhat out of date, in view of the decade's development in this feature of the coal-mining industry. It should be explained that the present paper is limited to the use of mining-machines in bituminous mines. Practically all of the anthracite mined is "shot from the solid," no undercutting being done. Anthracite-mining is therefore not considered in the statistics or other references. The statistical record as compiled by the U. S. Geological Survey shows that in 1898, the year preceding the presentation of my former paper, there were 32,413,144 short tons of coal undercut by the use of machines. In 1907 the machine-mined coal-product amounted to 138,547,823 short tons. In sympathy with the general decrease in coal-production during 1908, the output of machine-mined coal decreased to 123,183,334 short tons, but the proportion of machine-mined coal to the total output, nevertheless, showed an increase, from 35.1 per cent. in 1907 to 37 per cent. in 1908. In 1898 only 19.5 per cent. of the total product was unclercut.by the use of machines. The number of in use in the bituminous mines of the United States has increased from 2,622 in 1898 to 11,144 in 1907, and to 11,569 in 1908. The total production of bituminous coal in the United States in 1908 mas almost exactly double that of 1898, while the machine-

Jan 1, 1911

By William H. Shockley

Though China has been widely explored by mining engineers during the past dozen years, comparatively little has been published concerning its mineral resources. The few moilographs scattered through the transactions of various societies contain far less information than the private reports made to the numerous syndicates which have sent out engineers. The best general account of the geolopy and mineral resources of China is to be found in the works of von Richthofen,' a remarkably gifted observer. The observations recorded here in this paper were made in the service of the Pekin Syndicate (which has kindly given me permission to publish them), during the first months of 1898, among the coal- and iron-fields of southeastern Shansi. This is one of the largest anthracite-regions known, the area being

Jan 1, 1904

By Walter Miller

PETROLEUM refining, like other industries in the United States in 1940, focused much attention on its duties and opportunities in the field of national defense. In counter-distinction to the situation during the World War; the industry is well constituted as LO existing equipment, processes, and capacity together with planned additions to handle any demands that may be made upon it by the defense program needs. Evident throughout was the growing sense of ability to manipulate oil molecules for the production of materials not hitherto considered as being available commercially from petroleum The development and application of catalytically-induced reactions on a broad front is one of the distinguishing characteristics of refining progress during the year.

Jan 1, 1941

By George A. Miller

THE outstanding characteristic of the American business man is that he likes to run his own business his own way, without any interference from his wife, his friends, his bankers, and least of all from his government. The oil man, like the miner, is an American business man in which this special characteristic is even more pronounced. It may be because he has been an explorer and is more nearly like those pioneering Americans who explored, developed, and built these United States.

Jan 1, 1944

By T. A. Rickard

The interior of West Australia is an arid table-land, elevated 1400 feet above the sea. This plateau is flanked to the south by the Tertiary limestones which fringe the Great Australian Bight. It is bordered northward by the Carboniferous beds of the Fitzroy river and westward by the granite of the Darling hills, while to the cast this wide area, about 900 miles square, slopes downward imperceptibly into an undulating plain of sand, which stretches with dismal persistence across the boundary of South Australia. The waters of the ocean receded from this tract of land long ago; it is probably the oldest landsurface on the globe, and represents the basal wreck of a much larger continent. Fig. 1 is a map of this region. The Coolgardie and Kalgoorlie gold-fields are situated in the southwestern part of the region. The rock-formation consists of granite penetrated by diorites and andesites. The latter are occasionally associated with tuff's, which have been readily mistaken for sedimentaries. There are no fossil-bearing rocks, such as would afford a datum-line from which to measure the relative geological age of the prevailing formation. On the extreme edges of the mining territory there are, it is true, remnants of sand-rock which are considered identical with the " Desert Sandstone " of Queensland, determined by Daintree to be of Mesozoic age. But even this formation has evidently been laid down so long subsequent to the underlying rocks that it serves merely to emphasize their much greater antiquity. In their characteristics and in their relations to each other, the granite and the diorite of the Coolgardie region appear to me much to resemble the Laurentian granite and the Huronian

Jan 1, 1899

By F. V. Lene, E. J. Westerman

The recrystallization behaviors of two extruded and cold-drawn experimental sintered aluminum powder alloys, containing 1.75 and 3.0 pct Al2O3 by weight, were compared with that of extruded and cold-drawn commercially pure alumirzum. The kinetics of recrystallization of the alloys are described semiquantitatively. For the alloy containing 1.75 pct A l203 the rates of nucleation and of growth were also semiquantitatively determined. THE most striking property of aluminum alloys strengthened by a dispersion of Al2O3, the so-called SAP alloys, is their stability at elevated temperatures. One of the manifestations of this stability is their resistance to recrystallization after they have been cold worked. Most of the commercial grades of either the Swiss SAP or of Alcoa's Aluminum Powder Metallurgy Products have not been recrys-tallized after cold working, even when they are heated for a long time at a temperature near the aluminum melting point. Lenel, however, observed that the dispersion strengthened aluminum alloys with a larger spacing between the oxide particles than that of most commercial grades would recrys-tallize.1 It appeared to be of interest to further investigate the mode and kinetics of recrystallization of these alloys, and to compare their recrystallization behavior with that of commercially pure aluminum. Because homogeneous deformation of these SAP alloys in tension did not provide sufficient cold work to induce recrystallization, they were cold worked by wire drawing; the nonuniformity of this deformation unavoidably complicated the interpretation of the recrystallization studies. EXPERIMENTAL DETAILS Extrusions—Two types of sintered aluminum powder extrusions were used in this study. One type, designated AT-400, was produced from Reynolds atomized aluminum powder consisting of spherical particles averaging 3µ in diam and containing 1.75 wt pct of Al2O3. This powder was very similar to the R3M powder from which extrusions were previously prepared with an average spacing of 0.9µ between oxide particles.2 The second type, designated MD 2100, was produced from Metals Disintegrating Co. flake powder containing 3.0 wt pct of Al2O3, with an average flake thickness of 0.8µ. The average spacing between oxide platelets in MD 2100 extru- sions was 0.45µ.2 Powder compacts of 3/4-in. diam were extruded at 1000°F into 0.097-in. diam (AT-400) and 0.093-in. diam (MD 2100) wires by methods previously described.3 In order to compare the recrystallization behavior of sintered aluminum powder extrusions with that of wrought commercially pure aluminum 3/4 in. rod stock of 1100 F aluminum was extruded at 1000°F into 0.102-in. diam wire. Wire Drawing—Tungsten carbide dies were used for the AT-400 and 1100 F alloys. They had an included angle of about 15 deg and reduced the wire area approximately 7 pct per pass. Steel dies with an included angle of 11 to 13 deg and an average reduction per pass of 10 pct were used for drawing the MD 2100 alloy, because drawing this alloy through the carbide dies produced overdrawing defects. Heat Treatment—The cold-drawn wires were cut into small samples, and the deformed ends were etched off. The samples were each wrapped tightly in a single layer of aluminum foil, and individually isothermally annealed in a lead bath. Metallography—The modes and kinetics of recrystallization were determined by metallography. Mounted and polished specimens were anodized in a solution of 1.8 pct HBF4;4 examination under polarized light clearly revealed their grain structures. The recrystallized grains were generally much larger than those of the unrecrystallized matrix, and could clearly be distinguished because they alternated between maximum and minimum light reflection when the microscope stage was rotated, while the unrecrystallized matrix had a comparatively homogeneous "salt and pepper" structure. The fractional recrystallized volumes of the dispersion hardened alloy wires were determined by cutting and weighing of recrystallized and total transverse areas on photomicrographs. The recrystallized grains in the 1100 F alloy were too small to be cut out individually; therefore a combination of cutting and lineal analysis was used in this case. RESULTS AND DISCUSSION Modes of Recrystallization—The modes of recrystallization of the three alloys varied widely. In the 1100 F alloy nucleation and growth started in the region midway between the center and the surface;

Jan 1, 1961

By U. F. Kocks

The flow stress in some latent slip systems of aluminum and silver crystals after various deformations in single slip was investigated by transverse compression and supplemented by experiments on overshoot of the compression axis and the stability of corner orientations. Work hardening was found to be remarkably isotropic, the ratio of the flow stress in the latent system to that in the primary system being between 1.0 and 1.3. The strain-rate dependence was not significantly larger in the latent system. This low anisotropy suggests that specific dislocation interactions are not the direct cause of work hardening. Either the obstacles are essentially impenetrable so that only their distance enters, or a fairly random distribution of dislocations of all systems is. in fact. formed during single slip. The latter seems to he excluded by the observations on the strain-mte dependence and on the amount of secondary strain. The amount of seconzdary strains occurring in single slip was determined by shape-change mensurements and by a new method connected with the latent-hardening experiments. It is definitely less than 1/300 times the strain in the primary svstem. WORK hardening is due to dislocation interactions; this is a hypothesis, and possibly the only one, on which all present work-harden ing theories agree. About a dozen specific interactions have been considered, and it is unlikely that any essential one has been missed. Different work-hardening theories differ to a large extent in the specific interactions which are deemed most important. The presence or absence of any particular interaction, and its degree, depend on the geometrical relationships between the two dislocations interacting. Let us enumerate some examples. Two dislocations may react, with a varying reaction energy, to form a third dislocation, and this reaction product may be sessile or glissile. Two dislocations may intersect and a jog may be formed on both, on one of them, or on neither; this jog may be sessile17Z or glissile and it may, if moved nonconservatively, lead to the production of vacancies or interstitials. Finally, a dislocation may bypass another one and thus interact only with its stress field. All these interactions depend on the specific relation between the Burgers vectors and line directions of the two dislocations. Any dislocation generated during plastic deformation of fcc crystals belongs to one of twelve slip systems. Taking any one dislocation, its relationship to each of the other eleven can fall, by symmetry, into one of only five classes. These relationships are enumerated in Fig. 1 and Table I. Each slip system is represented in the stereo-graphic projection by two triangles, namely those in one of which the specimen axis would have to lie if the specimen were to deform in single slip on this slip system in a given sense, in a tension test. Let us represent the primary slip system by the shaded triangles. The other slip systems are classified only with respect to their relationship to this primary system. The code letters (initials of established names* in German) are explained in Table I. Three specific interactions are also listed in cases where they may be strong: the product of a reaction, the formation of jogs in either system, and the elastic bypass stress. The last column relates to the types of experiments reported in this paper and summarizes their results. To decide experimentally between the relative importance of the various interactions one would like to produce a group of dislocations in one slip system and then measure the stress necessary to force another group of dislocations of a specific second system through them. Hopefully, one can produce the first set of dislocations by plastically deforming the specimen in single slip. Then one can try to achieve single slip in a specific, previously latent system and measure its flow stress. If it is different from the virgin flow stress, there has been "latent hardening". Some types of latent-hardening experiments will be discussed in the next section. The strain-rate and temperature dependence of the flow stress is an indication of the importance of dislocation intersections. By extending an investigation of this dependence to the latent systems, one can determine how much more important forest contributions are here. seeger3 has used the as-

Jan 1, 1964

By J. M. Boutwell

PAGE I. Introduction,.......541 II. General Geography,......542 III. General Geology,......544 1. Sedimentary Rocks,..... 544 2. Igneous Rocks,...... 545 3. Areal Geology,.......546 4. Structural Geology......547 IV. General Character of Ore-Deposits,...548 V. Genesis of the Disseminated Ore in Monzonite,.... 549 1. General,........549 2. Character and Occurrence,... 649 3. Genesis,....... 550 4. Superficial Alteration.....553 5. Conclusion......553 VI. Genesis of the Ore in Fissures,...553 1. Character........... 553 2 Occurrence......554 3. Deposition...... 556 4. Transporting Agent....555 6. Immediate Causes of Deposition..556 6. Superficial Alteration....564 7. Conclusionl ..... 565 VII. Genesis of the Copper-Ore in Limestone...... 566 1. Character......566 2. Occurrencel .....566 3. Deposition......567 4. Relation of Fissures.....569 5. Relation of Intrusives,...571 6. Superficial Alteration....575 7. Conclusion......578 VIII. Periods of Ore-Deposition....578 IX. Dates of Mineralization.....579 X. General Conclusions.....580 I. Introduction. The object of this paper is to present a concise statement on the genesis of the copper- and lead-deposits of the Bingham

Jan 1, 1906

By Arthur G. Levy, Henry M. Howe

$1. Introduction.—Any given piece of metal is made up of a very great number of grains, usually microscopic, each of which is a perfect crystal save only in outward form, with cleavage planes of low cohesion, geometrically arranged quite as in fie familiar non-metallic crystals. The plastic deformation of such a mass occurs chiefly through the slipping of the crystalline blocks of which each grain is composed along these cleavage planes, causing steps called slip bands to form on a previously polished surface. In this slip, the metal immediately adjoining each of the cleavage planes along which the slip takes place is thought to pass extremely rapidly through a very mobile state into the amorphous state, in which it is harder than the remaining still crystalline metal between the amorphous layers thus formed along the slip planes. Whether the slip planes below the surface in ferrite can be detected by cutting, polishing, and etching sections is in dispute; but if this detection is possible at all, it is usually made impossible by heating the metal even gently. In short, the change along the slip planes does not persist through heating, and it is thought not to persist through time even at the room temperature, nearly all the amorphous metal recrystallizing. The network in Fig. 22 and the parallel N.-70-E. lines in Fig. 21 are slip bands in copper. When plastically deformed metal is heated, certain parts of certain grains may twin, that is, their component crystalline units may rotate into a position, or more exactly into an orientation, symmetrical with the initial orientation and hence with that of the remainder of that grain. As seen in a microsection of a metal the twinned areas usually have parallel sides. The existence of twinning is recognized in metallic sections either by the presence of such parallel-sided areas differing in brightness from the adjoining metal, especially when seen under oblique light after etching, or more surely by the zigzagging of the slip bands which form when twinned metal is itself deformed again. Hence the usual procedure in developing twins is to deform plastically so as to cause the twinning tendency; to heat so as to allow the tendency to assert

Jan 1, 1915

By C. H. Gorski

A method for preparing titanium tetrachloride is described which consists of reducing rutile with coke and chlorinating the reduced product at 200° to 500°C. The crude distillate is purified by treatment with copper powder and distillation. Recoveries, exceeding 90 pct of the titanium in the rutile, were obtained. IN recent years considerable interest in metallic titanium has been aroused because of its outstanding physical and chemical properties. The present commercial processes for preparing titanium are modifications of the Kroll1 process and consist essentially of the reduction of titanium tetrachloride with magnesium in an inert atmosphere to produce metallic titanium with magnesium chloride as a byproduct. At present,' commercial titanium tetrachloride costs $0.32 a pound, which makes the price of the included titanium $1.28 a pound. As the titanium tetrachloride must be purified further before processing into metal, its ultimate cost obviously will be higher. Consequently, one of the prime requisites for the production of lower cost titanium metal is a source of low-cost titanium tetrachloride. Recently, Knickerbocker, Gorski, Kenworthy, and Starliper3 escribed a method for preparing titanium tetrachloride from low-grade Arkansas rutile by smelting the rutile with pyrite and coke to form a titanium matte and then chlorinating the titanium matte to prepare a crude titanium tetrachloride. This process had several inherent advantages. Low-grade rutile concentrates were utilized, the chlorination temperature was relatively low (approximately 200°C), and the reaction was strongly exothermic. However, this process had several disadvantages, chief of them being the rather low recoveries of titanium tetrachloride (65 to 81 pct) and the difficulty in purifying the crude titanium tetrachloride obtained. Because of the high-titanium and low-iron con- tents of rutile as compared to ilmenite, rutile should be of greater potential value as a source of titanium tetrachloride than ilmenite. Rutile, however, is not chlorinated directly in commercial practice, because reaction temperatures above 700 °C are required, at which point chlorine attacks most of the common materials of construction. The process now in use consists of converting the titanium in rutile to the cyanonitride by high-temperature reduction in an electric furnace, and then chlorinating this compound. The disadvantages of this process are the difficulty of producing the cyanonitride, the use of high-grade rutile concentrates in the charge, and the presence of several percent of silicon tetrachloride in the finished product. It would be of considerable interest to develop a new process for the preparation of titanium tetrachloride from rutile by chlorination at 200" to 500°C. Process Development Several investigators'-' have studied the reduction of titanium dioxide with carbon in an effort to prepare titanium monoxide. Invariably, the titanium monoxide formed in this manner was not pure, as it contained titanium carbide and one or more of the lower oxides of titanium. As these lower oxides of titanium are more reactive chemically than rutile, and as it is known that titanium carbide may be chlorinated readily, a study was made of the chlorination of carbon-reduced rutile. A sample of rutile concentrates from Hot Spring County, Ark., containing 76.19 pct TiO,, 5.65 pct Fe2O3, 4.18 pct SiO2, and 2.88 pct Al2O3, was used for this investigation. The experimental procedure consisted of making an intimate mixture of —100-mesh rutile and petroleum coke, adding water and molasses as a binder to foi-m a paste, charging into a graphite crucible that was covered, except for a vent to allow the

Jan 1, 1952

By Thomas Henderson

Strategically, intermaterials competition is important to companies involved in raw materials extraction, smelting, refining or other processing, semi-finished and finished goods fabrication, and end-use consumers. In other words, just about every company involved in manufacturing. The array of materials covered by other papers in this session is testimony to the subject's breadth. In trying to provide an over- view of such a broad topic, the purpose has been to relate some of the common characteristics of the markets, economics and technology of raw materials, and to describe some of the ways in which Intermaterials competition impacts the markets, economics and technology of raw materials.

Jan 1, 1982

By John T., Ryan

THE subject assigned me, "Safety in Mining," is a very broad one and only the high spots can be covered in this short paper. As this is a meeting of the Coal Division, these remarks will be directed largely to coal mine safety, although the principles of safety and effective accident prevention methods are relatively the same in every branch of mining or industrial work. The coal mining industry should take pride in the part it has played in the development of the accident prevention movement, and there is ample proof for the statement that the first real organized accident prevention, work, both abroad and in this country, was con- ducted in the coal mining industry.

Jan 1, 1930

By C. Schlumberger

SINCE the beginning of .the year 1928 the senior authors and their associates have applied a series of procedures which makes possible the detailed study in situ of the formations traversed by a drill hole before the casing has been landed. They have given the name "electrical coring" to the ensemble of these processes, which now replace in a large measure the mechanical coring performed by the drillers, and permit the gathering of bottom-hole data hitherto unobtainable. Three years have elapsed since the technique and interpretation of these measurements emerged from the experimental stage and entered the field of industrial application on a large scale. The total length of drill holes so far surveyed by the authors and their associates, all over the world, amounts to several millions of feet. Practical and strongly built equipment has been evolved, which permits the examination in a short time of an open hole several thousand feet long. No comprehensive paper has yet been published discussing the essential principles of the processes applied and bringing into evidence their economic interest. This is the object of the present paper.1 Numerous examples of field work performed under varied geological conditions are given, constituting a concrete illustration of the services rendered by the new methods. The study in situ of the formations penetrated by a drill hole is based on the measurement of a given physical factor or parameter associated with these formations. Generally. the measurements are made syste-matically along the whole length of the open hole. The physical factors or parameters which are now utilized by us to this end are: (1) the resistivities of the rocks; (2) their porosity; (3) their electrical anisotropy; (4) their temperature; (5) the resistivity of the muds. In order to

Jan 1, 1932

By R. J. Wasilewski

The variation of elastic modulus with terrzperature between -150° and 600°C has been investigated. Compounds close to equiatomic cornposition exhibit very low modulus values and very high damping near room temperature. The modulus rises steeply with both decreasing and increasing temperature. The modulus minimum and the high damping are believed to be connected with a martensitic transformation of TiNi. In bulk material this transition takes place slightly above room temperature quite rapidly and reversibly, with a hysteresis of some 30°C, depending on the Ti:Ni ratio. Oxygen impurity affects the reaction time. THE inter metallic compound TiNi has been reported to exist in an ordered CsCl (B2) structure,l-6 the homogeneity range varying rather markedly with temperature.7 Some investigators reported this compound to decompose peritectoidally to Ti2Ni and TiNi, between 650° and 800°C,3 or below,',g the latter workers also suggesting the decomposition to be strain-sensitive. Purdy and Parr were the first to report a structural transformation to a new, possibly hexagonal, structure at 36°C,7 a temperature indubitably too low to allow the significant amount of diffusion necessary for a peritectoid reaction. Mechanical-property investigations of compositions close to TiNi just above room temperature have qualitatively shown remarkable anomalies, particularly with respect to clamping,' and to a "memory" effect, that is, plastically deformed material returning to its original shape on being heated through the "decomposition" temperature.9 The original explanation of this effect—based on the apparent experimental observation of Ti2Ni or TiNi, formation in the material subjected to tensile or compressive stresses, respectivelp—does not appear plausible. It appeared more probable that the change involved may be a martensitic, diffusionless structural transformation, similar to those observed in other B2 structures such as 0 brass,'' AuCd,ll and AuZn.12 The existence of such transformation has been established recently,', although the symmetry of the low-temperature structure is not yet known. The present paper describes the elastic modulus and damping behavior of polycrystalline TiNi in both structures. EXPERIMENTAL METHOD 1) Specimens. All the specimens to be investigated were prepared from premelted electrolytic nickel and iodide titanium by nonconsumable arc melting and casting in a water-cooled copper mold. The cast billets were canned in mild steel, extruded, and swaged to approximately 0.375 in. diam. The cans were then removed by pickling or machining. Preliminary material balance checks indicated no significant weight losses on melting (less than 5 mg on a 50-g button); hence nominal compositions have been used throughout. In agreement with previously reported observations7 no single-phase material was obtained at—or close to—Ti 1.00 Ni1.00 a small amount of finely divided second phase always being present. It was found that most of the oxygen impurity was associated with this minor phase, which was identified as oxygen-bearing Ti2Ni—possibly Ti,Ni,O. The amount of this phase—at any given Ti:Ni composi-

Jan 1, 1965

By LIONEL E. BOOTH

ORE tests are made for the purpose of determining the correct methods of treatment for any particular ore. They should be conducted so as to insure that the results obtained in actual mill practice, on ore of similar grade and physical nature, will duplicate the results obtained in the test work. As the expenditure of many thousand of dollars may be involved in the building of the necessary mill, the testing of ores calls for extreme care and skill in handling laboratory machines, and a knowledge of actual practice to guard against the danger of obtaining results in test work that would be impractical to duplicate on a commercial scale. The importance of a correct sample of the ore is at once apparent. No matter with what degree of care the test 4rk is done, it loses its value when made on an unrepresentative sample. It is the first safeguard against future disappointments in the loss of capital and time. A number of failures in the past have been traced directly to faulty or lax methods in obtaining the ore sample.

Jan 1, 1924

By AIME AIME

THE quarters provided for the session on Milling Methods, Monday afternoon, Feb. 17, were filled to capacity. Galen H. Clevenger presided and notables, such as A. W. Fahrenwald, A. O. Gates, F. A. Thomson, W. L. Zeigler and others who had not graced a milling meeting in New York in recent years, or per- haps even never before, were actually present and spoke "in person." The first paper, by A. W. Fahrellwald (T. P. 275), entitled "Classifier Efficiency ; An experimental Study," was summarized by the author, who clearly showed the inconsistency of determining the efficiency of a classifier by means of sizing tests, especially where the material classified consists of a mixture of minerals of different specific gravities. In place of sieve analysis the procedure recommended involves the use of a glass settling-tube which is considered to give ideal classification and thus serve as a standard against which mill classification will be compared and relative efficiency calculated. This procedure sounds logical. Perhaps the greatest difficulty may lie in securing an ideal classifier acceptable to every one.

Jan 1, 1930

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By John T. Norton, Robert J. Anderson

The purpose of this paper is to report evidence, regarding metal structures, that is contradictory to the amorphous-metal hypothesis of Beilby, and particularly evidence that is opposed to the proposition that a vitreous amorphous layer is produced by polishing a piece of metal. According to the theory of Beilby, which has been developed by Rosenhain and others, polishing a piece of metal greatly affects the condition of the metal at or near the surface polished, making that surface entirely different in character from the metal beneath. A vitreous amorphous surface film is said to be formed. The polishing process, on the basis of Beilby's explanation, is well known and does not require discussion here, but it is advisable to seek the precise meaning of the term "amorphous." According to Beilby, "amorphous means non-crystalline in the most intimate sense of the word; the molecules arc not marshalled in crystalline order and orientation." According to Rosenhain, the amorphous condition is that assumed by a metal when the crystalline arrangement is completely broken up so that the atoms exist in a state of disorderly arrangement similar to that which exists in the liquid state. Thus, from the point of view of the phase rule, the "amorphous phase" is regarded as being identical with the liquid phase. Amorphous metal is often likened to an undercooled liquid. A crystalline substance is one in which the atoms are arranged in space according to some definite repeating geometrical pattern. The existence of amorphous metal has not been definitely proved. The evidence offered here that amorphous metal probably does not exist is of a direct nature and is afforded by x-ray diffraction effects given by a number of metals and alloys when polished, cold-worked, and annealed. Considerable of the experimental work was carried out with substantially pure aluminum and the aluminum alloy duralumin, but many of the observations made on these materials were checked by similar observations on copper, iron, tin, zinc, lead, mild steels, and

Jan 1, 1925

By O. N. Carlson, W. M. Paulson

A phase diagram is proposed for the Y-C system based on the vesults of thermal analyses, microscopic obsevvations, and X-ray diffraction studies. Three intermediate phases occur in the system: a congru-ently melting fcc phase with a wide range of homogeneity about the composition Y2C, an intermediate solid-solution region between 55 and 58 at. pct C, and a bct dicarbide melting congruently at 2415°C. All three compounds undergo a phase transformation at elezlated temperatures. A continuous serzes of solzd solutions exists between the fcc phase and the high-temperature form of YC2 with a maximum in the solidus at 2000°C and 30 at. pct C and a minimum at 1805°C and 54 at. pct C. THIS investigation of the Y-C system was undertaken as part of a nuclear materials development program. Yttrium-base alloys are of interest as possible containers for liquid metals, and carbides are currently receiving increased attention as high-temperature materials for advanced reactors and other applications. Previous work on this system was limited in scope, and the results were somewhat inconclusive and at times contradictory. Spedding et al.&apos; reported the existence of a triyttrium carbide having an fcc structure with a wide range of homogeneity and Dean et a1.2 reported the existence of a rhombohedra1 phase having the stoichiometry of Y2C. Bachella et a1.3 observed that the latter was the result of ordering of carbon atoms in the fcc solid solution. The ordering range was placed at 800" to 1000°C. Vickery et a1.4 reported a high-melting compound which they identified as yttrium dicarbide, and Spedding and coworkers1 determined the structure of this phase as bct with lattice parameters a = 3.66 and c = 6.17A. Samsonov et al.5 reported the melting point of YC2 as 2300" * 50°C. Recently Bowman et a1.6 found a transformation in the dicarbide from the tetragonal to an fcc form at 1320 20°C. Samsonov and coworkers7 reported a monocarbide of yttrium melting at 1950" * 20°C and also a sesqui-carbide melting at 1800" * 50°C. The existence of the latter has also been indicated by others,1&apos;8 but neither compound has been definitely established. The Y-C phase diagram shown in Fig. 1 was proposed by Chubb and Keller8 in 1964 based on the data available at that time. The tentative nature of this diagram together with the uncertain status of the compounds indicated that additional work on this system was needed. EXPERIMENTAL PROCEDURE Yttrium metal of 99.9 pct purity was prepared for use in this study by the reduction of YCl, with calcium to form a sponge product.9 The major impurities in this material were as follows: 100 ppm C, 150 pprn H, 20 ppm N, 300 to 1000 ppm O, <20 ppm Ca, <100 ppm Cr, <80 ppm Cu, 150 ppm Fe, <30 pprn Mg, <400 ppm Ta, and <100 ppm Ti. Alloys were prepared by arc melting yttrium sponge together with pieces of high-purity graphite rod in a purified argon atmosphere. Homogeneity was insured by repeated melting, inverting the ingot between melts.

Jan 1, 1969