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By R. V. Wheeler, F. V. Tideswell

The suggestion, which appears to find increasing favor, that the elementary composition of coals should be used as the basis of their classification, makes it important that our methods of expressing this elementary composition should be refined. It is doubtful whether many published ultimate analyses of coals are accurate within 1 per cent. carbon. Many are probably as much as 3 or 2 per cent. in error in carbon. It is, perhaps, not always realized that the extreme variation in carbon content over the range of bituminous coals is but 16 per cent. An error of 1 per cent. in carbon on analysis corresponds therefore with one-sixteenth of the whole range, an amount which is unjustifiable even for the application to commercial needs of a system of classification based on ultimate analysis. For the purposes of scientific research such limited accuracy is of little value. The object of this paper is to examine one important source of error in ultimate analysis, that due to the occurrence in coal of inorganic material, and to emphasize the need for the quantitative measurements (of carbon more particularly) on coals to be rendered independent of their contents of such material. Adventitious Mineral Matter When a determination of calorific value, for example, is made upon a coal, it is customary to correct the measured value with respect to the ash left by the coal on incineration, recording the result as being on an "ash-free basis." It is desirable, before discussing the adequacy of the correction thus made, to demonstrate its validity, which turns on whether the ash is present as an adventitious impurity in the coal and forms no part of the coal substance itself. The inorganic matter associated with coal has originated in several ways1: 1. The "inherent" inorganic materials, occurring as constituents of the plants from which the coal-forming deposits were derived.

Jan 1, 1928

By M. Gensamer

ALTHOUGH a large number of X-ray photograms of cold-rolled steel have been published, two circumstances have led to the experimental work reported in this paper. The first is that no complete study, making use of the pole-figure method of Wever1, has been made of cold-rolled low-carbon steel. Wever has published pole figures of mild steel sub-jected to plane parallel deformation1,2 and undoubtedly he has applied the method to cold-rolled mild steel, but the authors have not found these data published. Kurdjumow and Sachs3 have applied the method to the study of rolling and recrystallization textures in electrolytic iron; their results will be referred to later. The reason for this dearth of papers using the pole-figure method is obvious; a greater number of photograms and more analytical work (although this work is quite simple and straight-forward) are required to construct a pole figure than most investigators have felt worth while, despite the fact that no other method of which the authors are aware will satisfactorily depict the orientations of the crystal-lites in a polycrystalline aggregate. The second circumstance that led to the work reported in this paper was the appearance of a paper by Wayne A. Sisson4 on the same subject. In his valuable study of the factors influencing the development of pre-ferred orientations in cold-rolled mild steel, Sisson made one observation that required confirmation; that is, that at some stage of the rolling proc-ess the type of preferred orientation changed from the type that gives a photogram characterized as a "six-point" X-ray pattern to that known as a "four-point" pattern. A similar observation had been made by Tam-mann and Heinzel5, who studied the orientations developed in the rolling of steel by the specular reflection of light from the etched surface of rolled samples. These workers also found that the type of preferred orientation

Jan 1, 1936

By Wheeler P. Davey, Robert T. Phelps

A study of solid solutions has long been a source of interest because of the conditions controlling their formation. X-ray investigations so far have been conducted with the idea that there were two types of solid solutions. In the first type, an atom of the solute was supposed to replace an atom of the solvent in the crystal lattice. In the second type, an atom of the solute was supposed to lie in one of the interstices between the atoms of the solvent. These pictures both require that the sizes of the atoms must play an important part in the process of solution. It is the purpose of the present investigation to study the mechanism of solid solution, using pure silver as the solvent, and pure aluminum as the solute. X-ray measurements show that these elements have the same "shape" of atomic domains1 (they both crystallize as face-centered cubes) and that their atomic diameters differ by less than one per cent.' The results of the present investigation point toward a chemical rather than a physical picture of the nature of solid solution, and make the older pictures merely special cases of a more general picture. The new theory has the advantage, too, that it offers a rational explanation of certain phenomena which hitherto have been only interesting detached facts. The aluminum-silver system which was chosen for this study has been studied by various methods by several workers. By means of thermal analysis Gautier2 and Petrenko3 have determined the phase diagram. Hansen studied the aluminum-rich alloys by means of thermal and microscopic analyses. He showed that at high temperatures silver dissolved in aluminum to the extent of 47 per cent by weight at 560" C. But this solubility decreased to 1 per cent at 200" C. Westgren and Bradley5 made an extensive X-ray study of these alloys. They used the change in the lattice parameter of silver as a criterion of the solution State College, Pa.

Jan 1, 1932

By J. C. Jaeger

The study of brittle fracture of rocks has been a much neglected subject until quite recently and now is in a state of transition and rapid development. Historically, three methods of testing were used by engineers: uniaxial tension, bending, and, by far the most common, uniaxial compression of cubes. This latter was probably adequate for engineering requirements, but from the last century onwards there has been a demand from geologists for a study of the properties of materials under conditions comparable with those at depth in the earth's crust. King1 remarked that "in engineering practice a cube of the material is put into a testing machine and the stress required to crush the cube is measured. This gives the limiting stress difference for the material so long as the boundary conditions are similar to those existing during the test . . . this may by no means be the case when the boundary conditions are very different from those existing in the test, for instance, in the case of rupture in the neighbourhood of a cavity. . . ." Despite this very clear statement of principle, many writers until recently (e.g. Jeffreys2 used the uniaxial compressive strength as a measure of the 'strength' of rock. In the last century (Becker 3, it was both conjectured and, for some rocks, known qualitatively, that plastic deformation could occur under confining pres- sure; the demand from geologists has been for the study of flow rather than fracture of rocks.. From the time of von Karman (1911) and Böker5 (1915) onwards, apparatus has been built which could provide confining pressures sufficient to make some rocks plastic. Many experiments tended to be made on rocks such as marble, which readily become plastic, and the general tendency was to make relatively few experiments in the brittle range. This is particularly true of many experiments on combined stresses. As a result of this, there is not sufficient data to provide adequate information

Jan 1, 1967

By V. F. Parry, S. P. Burke

The presence of gas in coal mines necessitates the use of costly ventilation arrangements and the use of expensive mining methods. On the other hand, the gas itself in many instances is of considerable intrinsic value, and its separate recovery might conceivably be a profitable undertaking. This paper is concerned with a study of the movement of gas in coal strata with the object of determining the laws governing gas movement and thus making at least a preliminary step toward the solution of the more practical problem of its control or recovery. Naturally, so important a subject has received much attention from scientists and engineers. In most cases, however, the studies have been concerned with the origin1$, the amount" the composition3 and the method of retention4 of the gas in coal; or, from the more practical side, have been concerned with the phenonlena and conditions associated with outbursts5 or explosions and their control. Numerous studies also have been made of the permeability of coal to gas" of gas pressures measured in coal seams, etc. The authors are unaware, however, of any attempt to present a consistent or complete picture of the laws governing the movement of gas through the coal. Study in West Virginia A recent study conducted at this University7 gives the first presentation of the distribution of pressures in a small section of a coal seam. Holes were drilled into the coal rib to various depths and at various distances from the coal face. The location selected for study was as remote as possible from disturbing influences of mining operations, faults, "wants," etc. The pipes extending into the coal that were used to determine pressures were grouted into the borehole for the entire depth of the hole, and great precaution was taken to insure accurate pressure readings. A map of the geology of the region, a map of the probable boundary and extent of the coal seam, a current map of the mine and a

Jan 1, 1936

By V. F. Parry, S. P. Burke

The presence of gas in coal mines necessitates the use of costly ventilation arrangements and the use of expensive mining methods. On the other hand, the gas itself in many instances is of considerable intrinsic value, and its separate recovery might conceivably be a profitable undertaking. This paper is concerned with a study of the movement of gas in coal strata with the object of determining the laws governing gas movement and thus making at least a preliminary step toward the solution of the more practical problem of its control or recovery. Naturally, so important a subject has received much attention from scientists and engineers. In most cases, however, the studies have been concerned with the origin1$, the amount" the composition3 and the method of retention4 of the gas in coal; or, from the more practical side, have been concerned with the phenonlena and conditions associated with outbursts5 or explosions and their control. Numerous studies also have been made of the permeability of coal to gas" of gas pressures measured in coal seams, etc. The authors are unaware, however, of any attempt to present a consistent or complete picture of the laws governing the movement of gas through the coal. Study in West Virginia A recent study conducted at this University7 gives the first presentation of the distribution of pressures in a small section of a coal seam. Holes were drilled into the coal rib to various depths and at various distances from the coal face. The location selected for study was as remote as possible from disturbing influences of mining operations, faults, "wants," etc. The pipes extending into the coal that were used to determine pressures were grouted into the borehole for the entire depth of the hole, and great precaution was taken to insure accurate pressure readings. A map of the geology of the region, a map of the probable boundary and extent of the coal seam, a current map of the mine and a

Jan 1, 1936

By T. L. McCall

The late Walter Herd1 in 1929 gave a full description of past and present conditions in No. 2 mine, Springhill, Nova Scotia, developed theories regarding the cause of these bumps and made certain suggestions regarding possible methods of future development. Recapitulating briefly from Mr. Herd's paper, the seam is bituminous coal, averages 9 ft. in thickness and has a well defined parting containing fusain about 14 in. from the roof. This roof coal is somewhat stronger than the rest of the seam and has a tendency to cling to the roof. The pitch of the seam where it is now being worked is about 20". The first manifestations of bumps began when the room and pillar workings had reached a depth of cover of 1900 ft. and under continuously increasing depth of cover these bumps increased to such an extent, both in number and severity, that in the year 1924 it became apparent that some change in the system of extraction was necessary. After closely studying all the factors involved and benefiting largely by valuable outside advice obtained by the Provincial Department of Mines of Nova Scotia,2 the system of working was changed from room and pillar to longwall retreating. Mr. Herd's paper described in detail three remarkable bumps in the year 1928 in April, July and October that affected the 5700-ft. and 5900-ft. East levels, the last bump being so severe both in intensity and in extent of damage done that this district was abandoned. The longwall workings to the west of the slope had been stopped in the year 1926 owing to an inbreak of water, coming from the flooded waste of No. 3 seam lying some 400 ft. vertically overhead. This inflow was not excessive, but a large quantity of water being impounded in the old workings it was considered advisable to take the prudent course and not incur the risk of possibly increasing the flow by further working. This district has remained idle ever since.

Jan 1, 1934

By J. E. Burke, C. S. Barrett

THE fine lines shown in Fig 1 are typical of markings that may be detected after polishing and etching deformed specimens of alpha brass and other alloys. Although they have long been the subject of discussion by metallurgists their nature is still uncertain and the names that have been applied to them, such as deformation lines or strain markings, indicate this uncertainty. In this paper which reports the results of a further investigation of their nature, they will be called strain markings. INTRODUCTION Matthewson and Phillips1 in 1916 concluded that strain markings appeared only after deformations that exceeded 20 pct. They objected to the markings being called slip lines believing this term should be reserved for surface markings produced by plastic deformation. In 1921, Vogel2 described similar striations which appeared after polishing and etching the roughly ground surface of numerous alloys. He reported that the markings were crystallographic in nature, and since they resemble Neumann bands in iron, at least superficially, he assumed them to be mechanical twins. In 1928, Matthewson3 reported work by Phillips which indicated that the lines were more readily produced by impact than by slow deformation and that in many cases the twins inside recrystallized grains were parallel to strain markings in the original deformed grains. This was taken as evidence that the markings coalesce into annealing twins, and hence that they themselves are mechanical twins. Many attempts have been made to [ ] demonstrate directly that the markings are mechanical twins. In 1934, Samans4 described the results of X ray studies of two deformed crystals of alpha brass. Evidence was obtained which could be interpreted to indicate that the strain markings are mechanical twins, and this remains the only direct evidence to this effect. Several other attempts to obtain similar evidence by X ray diffraction have failed5,6,7 although in no case was the original method of Samans employed. An

Jan 1, 1948

By Howard Scott

Manganese being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Arg transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the As transformation occurs at a tem-pcrature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3, quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Arg point as falling to 0" C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer," sing alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 per cent for the manganese content at which As is depressed to 0" C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By P. W. Bakarian, C. H. Mathewson

THE greater part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation, in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)1 by geometrical analysis identified the {102} ? plane in magnesium as the twinning plane, Schiebold and Siebel (1931)2 confirmed this twinning plane, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also reported twin formation in a secondary role on the {101} plane. Schmid (1931)3 summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-i.e., the critical resolved shear stress-were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C., at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the original specimens of circular section had been

Jan 1, 1943

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By J. W. Halley

RIMMING steels derive their name from their action during solidifica-tion in the molds. As a result of incomplete deoxidation, gas is evolved during freezing, and the metal has a characteristic rolling action. The metal rises along the mold walls and descends in the center of the ingot. This action keeps the top of the ingot open and the advancing rim of solid metal can be seen. The rim grows until the rolling action is insufficient to prevent the top of the ingot from freezing or until the action is stopped by capping the ingot with a heavy plate. The violence of the reaction and its characteristics, such as growth or drop ill the molds, are deter-mined by the Composition, the furnace practice, and the deoxidation in the ladle and in the molds. Though rimming steels represent a large proportion of the amount of plain carbon steel made, they have received comparatively little attention in the technical literature. The manufacture of rimming steels has been described by Hibbard,1,2 Fleming,3 Pierce4 and Jackson.5 The reactions occurring during rimming have been considered from the theoretical point of view by Chipman and Samarin.7 The structure of rimmed-steel ingots has been discussed by Nead and one of the present authors.6 Meyer,8 in studying segregation, investigated the distribution of carbon, sulphur and phosphorus in rimmed-steel ingots by analyzing the rim and core of blooms. In their studies of segregation, the Joint Committee of the Iron and Steel Institute and the British Iron and Steel Federations studied distribution in one billet and one ingot of rimmed steel. A detailed study of the distribution throughout the ingot has not been published. The present investigation was undertaken to determine accu-rately the distribution of carbon, manganese and sulphur in normal rimmed ingots and the general distribution of other common elements present. The study included some work on the effect of pouring condi-tions and furnace practice on the distribution, though there is still much to be done in this direction.

Jan 1, 1938

By Robert E. Tally

Underground fires have been common in the mines of the United Verde Copper Co. for the past 22 years. The first fire started in the 300 Hampton stope in the fall of 1894, following a cave in that orebody. The soft and highly pyritic nature of the ores is responsible for most of these fires. Since ore characteristics, methods of mining and ventilation, have an important influence on mine fires, they will be described in this paper. Orebodies The ores are mostly chalcopyrite except on the upper levels where considerable chalcocite, black oxides and other secondary minerals occur. The orebodies are in the form of lenses and vary in size. Some are small, while others are several hundred feet in length by a hundred or more feet in width. These orebodies extend, in some cases, from the surface to the lowest levels of the mine and usually at a steep angle of inclination. There are three different classes of ores, classified in accordance with the gangue rock. The copper in all cases, except as above specified, is in the form of chalcopyrite. The largest and most important of these reserves are in a pyrite gangue. Next in order of importance are the schist ores and lastly the quartz porphyries. The pyrite, locally termed iron ores, average from 30 to 42 per cent. sulphur. The schist and quartz porphyries vary from 3 to 25 per cent. sulphur. Mining Methods All the orebodies were worked by the overhand square-set method of mining prior to 1908; since then the cut-and-fill, shrinkage and mill-hole systems have been largely employed. But 15 per cent. of the total tonnage now extracted is from timbered stopes. Most of this is from the upper levels where the ore is soft, heavy and more or less broken to the surface. Large reserves of these ores are being conserved for more efficient methods of mining.

Jan 1, 1917

By Walter E. Duncan, Oscar F. Tangel, A. M. Gaudin, Franklin Dewey, R. A. Johnson

Xanthates have been used as collectors of sulfide minerals in the concentration of ores by flotation for over a decade, yet much remains to be done to elucidate the underlying reasons for the remarkable effectiveness of these compounds in this connection. Briefly stated, the known facts concerning the effect of these reagents on the floatability of minerals are as follows: 1. Xanthates are without effect on silicates, silica, and generally on minerals currently regarded as "gangues." 2. Xanthates in very small amount increase enormously the floatability of sulfides of copper, lead, silver, iron and mercury. 3. If zinc sulfides are first '(activated," as by treatment with a copper salt, they are readily floated by xanthates; otherwise not. 4. Elemental copper, silver and gold have their floatabilities increased by xanthates. 5. Sulfides of elements that are not typically metallic—e.g., stibnite, realgar, molybdenit—are not made to float markedly better by treatment with xanthates. 6. Oxidized minerals of lead and copper are floated if treated with large amounts of xanthates, but not so if treated with amounts of the same order of magnitude as required for sulfide flotation. Oxidized zinc minerals are not floated unless xanthates having unusually long hydrocarbon chains (e.g., eight carbon atoms or more) are used. Iron oxides and carbonate are not floated by xanthates. From a flotation standpoint the most striking feature about xanthates is the very small amount required to accomplish startling changes in the behavior of some minerals. The amounts used in practice to effect excellent concentration are frequently of the order of 0.05 lb, of agent per ton of ore; that is, of the order of one part of agent per forty thousand parts of ore. Changes in amount of agent of the order of 0.01 lb. per ton of ore (or 0.002 lb. per ton of pulp, on a 4:l basis) have marked effects on the metallurgical results obtained. Yet these changes represent a variation of but one part per million parts of pulp.

Jan 1, 1935

By H. H. Stoek

Mine models have three distinct uses: 1. As exhibits in expositions and museums. 2. As exhibits in law suits. 3. As illustrations in teaching mining engineering. All three uses are in a sense educational. The third, or distinctively teaching function, has not been extensively developed in America as it has been abroad, chiefly because of the cost of the models and the scarcity of model makers. In connection with expositions, such as the Columbian, the Louisiana Purchase, and the Panama-Pacific, a number of very good mine and metallurgical models were prepared with funds furnished by State commissions, by mining organizations or mining companies. At the close of these expositions, some of these models have been deposited in National or State museums or in educational institutions, but too many of them haw been lost, or have been stored away in some mining company's office or in the basement of some State building, where they have been lost sight of and have gradually fallen to pieces. A visitor to a German mining school is impressed by two facts: 1. The mining laboratories are in general inferior to those in America. 2. The mining museums are infinitely superior to ours, particularly in models exhibited. One may reply to this comparison by saying that a museum is necessarily a work of time. From the historical standpoint this is, of course, true, but it is not necessarily true in connection with a working museum intended to illustrate current practice. For instance, the oldest mining school in Germany, that at Freiberg, has much excellent historical material, but very little on modern practice, while Berlin, one of the youngest German mining schools, has a most extensive and valuable collection of modern appliances and models. This is true in spite of the fact that one of the best-known model shops is at Freiberg, from which many of the models to be seen in America have come. Because many of the models in American mining schools have come from

Jan 1, 1918

By George A. Moore, Donald P. Smith

In spite of many investigations of the occlusion of hydrogen in iron, the nature of the process and the reasons for the accompanying effects upon the metal are still open questions. This is in large part due to three causes: (1) the difficulty of obtaining iron of adequate purity as starting material; (2) the occurrence of allotropic transformations, which complicate the effects; and (3) the fact that the body-centered cubic modification does not lend itself readily to crystallographic investigation. The present paper attempts a critical review and correlation of the somewhat scattered and disconnected existing observations, and an experimental determination of the extent to which the conclusions that appear to follow from these are applicable to iron of really high purity, studied under well-defined conditions. Review Although only a comparatively few investigations have so far been made on the pure system iron-hydrogen, there is a much larger volume of literature which throws some light on the problem but falls short of a place in the systematic investigations, either because no attempt was made to measure equilibrium conditions or because the metal used was not iron or the gas not pure hydrogen. Such results have been variously dismissed in the past as of no importance, or as too complicated to try to explain; or they have been explained in terms of any of a dozen or more pictures, each of which is contradicted by data from other sources. The present importance of these data thus arises from their very mass and diversity, which present a picture of occlusion as a phenomenon whose variability cannot be ignored. We have attempted to organize the literature into groups comprising similar experiments or data leading to similar conclusions, thus of necessity sacrificing accuracy of historical order. Lattice Occlusion.—Throughout this discussion, the term "lattice occlusion" will be used to denote the formation of a simple solid solution of a gas in a metal lattice, usually of interstitial distribution. The word

Jan 1, 1939

By George A. Moore, Donald P. Smith

In spite of many investigations of the occlusion of hydrogen in iron, the nature of the process and the reasons for the accompanying effects upon the metal are still open questions. This is in large part due to three causes: (1) the difficulty of obtaining iron of adequate purity as starting material; (2) the occurrence of allotropic transformations, which complicate the effects; and (3) the fact that the body-centered cubic modification does not lend itself readily to crystallographic investigation. The present paper attempts a critical review and correlation of the somewhat scattered and disconnected existing observations, and an experimental determination of the extent to which the conclusions that appear to follow from these are applicable to iron of really high purity, studied under well-defined conditions. Review Although only a comparatively few investigations have so far been made on the pure system iron-hydrogen, there is a much larger volume of literature which throws some light on the problem but falls short of a place in the systematic investigations, either because no attempt was made to measure equilibrium conditions or because the metal used was not iron or the gas not pure hydrogen. Such results have been variously dismissed in the past as of no importance, or as too complicated to try to explain; or they have been explained in terms of any of a dozen or more pictures, each of which is contradicted by data from other sources. The present importance of these data thus arises from their very mass and diversity, which present a picture of occlusion as a phenomenon whose variability cannot be ignored. We have attempted to organize the literature into groups comprising similar experiments or data leading to similar conclusions, thus of necessity sacrificing accuracy of historical order. Lattice Occlusion.—Throughout this discussion, the term "lattice occlusion" will be used to denote the formation of a simple solid solution of a gas in a metal lattice, usually of interstitial distribution. The word

Jan 1, 1939

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968

By Thomas C. Wilder

The concentration and activity of oxygen in liquid copper has been measured by the reversible galvanic cell: at 1100°and 1200°C for the concentration range of oxygen of 3 to 5600 ppm Measurements for approximately thirly alloys at each temperature indicate that the activity of oxygen roughly follows Henry's law, the activity coefficients of oxygen being 0.12 and 0.205 at 1100° and 1200°C, respectively. These results compare javorably with the results of seven other electrochemical and gaseous equilibrium studies on this system, the free energy of the solution reaction 1/2 O2 = O (7 at. pct in Cu, liq) being -18.10 * 0.30 kcal per gfw at 1200°C. Estimates of the standard molar free energy of formation of CupO(S) are also made. Praclicul consideration of this cell as an oxygen sensor for liquid metals is discussed briefly. SOLID mixed-oxide electrolytes which have a defect structure in the anion sublattice have recently become a very popular means by which the chemical potential of oxygen is measured at high temperatures. Since the pioneering work of Kiukkola and Wagner1 such electrolytes have been used in numerous cell studies for determining the thermodynamic properties of metallic oxides and oxy compounds, the partial pressure of oxygen in vacuum systems and other atmospheres, and the properties of oxygen dissolved in metals and alloys. The use of a solid electrolyte in a cell for a fast reliable method of oxygen determination in liquid metals would be a very important tool to the process metallurgist. In copper, for example, the oxygen content of the molten metal in the cathode furnace is a prime factor in determining the "set" or solidification profile of cast wire bars. In this investigation the activity of oxygen in liquid copper was measured by an electrochemical cell employing the electrolyte ZrO2 + 7 1/2 wt pct CaO. The cell used at 1100° and 1200°C was

Jan 1, 1967