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By Robert F. Mehl, Gerhard Derge

The gamma-alpha transformation in iron and iron-rich alloys is of such practical and theoretical importance that many papers have been published upon the subject relating to critical temperatures, transformation rates and accompanying property changes. Although crystallo-graphic studies are of less immediate practical usefulness, the opportunities which these offer to furnish data on the basic atomic movements which characterize the transformation are not to be neglected1. The early work on the crystallography of this transformation has been reviewed in the fourth paper of this series2; since then several important papers have appeared. Our present knowledge may be briefly summarized as follows. Kurdjumow and Sachs, working with a 1.4 per cent carbon steel3, established the orientation relationships subsisting between the face-centered gamma and the metastable tetragonal lattices in freshly quenched martensite, and between the face-centered gamma and the body-centered alpha lattices in tempered martensite. The orientation relationship observed in the latter case may be stated in terms of planes and directions observed to lie parallel in the two lattices: {111} ?//{110}a [110] ?// [111]a (This notation is used throughout as the most descriptive means of expressing the fact that any (111) plane of the gamma phase may be parallel to any (110) plane of the alpha phase, and that a [110] direction in a particular (111)? plane is parallel to a [Ill] direction in the corresponding (110)a plane.) From these relationships the atomic movements that transform the gamma lattice into the alpha may be inferred. In the present experiment these may be considered as consisting primarily in a shear of the atoms parallel to the {111} planes in [110]? Directions

Jan 1, 1937

By Hsun Hu, R. S. Cline

A detailed studj) of texture formation in 2 pet Al-Fe single crystals with initial orientations of approximately (111) [112], (112) [111], and (112) [111] was made by examining the textures developed on the surface and at various interior sections of the crystal after rolling to various amounts. Depending' upon the initial orientation of the crystal, the surface and interior textures may differ only in sharpness, or may differ essentially in orientation. The orientation of the (111) [112] crystal does not change upon rolling up to 70 pet, but after rolling more than 90 pet a distinct component of (001) (110] orientation is developed. The texture formed in the two (112) (1111 type crystals consists of (111) (1121 and (001) (1101 components. The latter, however, is largely confined to the surface layers. The textures formed on both sides of the crystal are identical, and the texture composition profile is approximately symmetrical with respect to the central section of the strip thickness. The formation of these texture components is analyzed. DURING the past seven or eight years, deformation and recrystallization textures in rolled Si-Fe single crystals have been extensively studied by various investigators.1-7 From these studies, much knowledge on texture formation in bee crystals of various initial orientations was obtained. However, these results also raised many questions, regarding particularly the correlation between deformation and recrystallization textures, as well as the deformation texture itself of some particular crystals. To take a (111) [112] type crystal as an example, it was shown by Dunn and Koh2, 3 that this orientation does not change during deformation by rolling. This finding is consistent with the conclusion reached by Barrett and Leven-son8 with respect to iron crystals that (111) [112] is one of the stable end orientations. However, different recrystallization textures were observed by Dunn and Koh3 in (111) [112] type crystals of different initial thickness, which widened differently during rolling even though their deformation textures were identical. Another interesting example, also from the results of Dunn and Koh2'3 is that of texture formation in a (112) [111] crystal. This crystal developed a two-component deformation texture of (111) [112] plus (001) [110]. Its recrystallization texture, however, was found to be predominantly (110) [001], which is related to the (111) [112] component by a simple [110] rotation. This crystal, therefore, behaved as if the other deformation texture component, (001) [110], were not present. There are also discrepancies among the results of different investigators, as well as numerous unexplained fine features of the deformation texture of crystals of various initial orientations. In order to have a better understanding of all of these points, a detailed study of deformation textures is greatly needed. One of the obvious things that has been completely overlooked in previous texture studies is the possible effect of surface texture. All past work on the texture of Si-Fe single crystals was conducted in a rather simple manner, i.e., the rolled crystals were etched to a very thin sheet; then their textures were examined by transmission X-ray techniques. For recrystallization texture studies, unless precautions are taken by etching off a sufficient amount of the surface layer before annealing, the texture developed in the interior may be affected by the surface layer, which may well have a different initial texture and which may have undergone recrystallization earlier than the interior of the specimen. Because of this effect, it is now planned to reexamine the texture of various rolled and annealed single crystals at the surface, and at various sections below the surface by using reflection techniques. In some cases, both surfaces of the rolled crystal will be examined. In one of Dunn's early papers,9 he noted that at an early stage of rolling the crystal seems to divide roughly through the middle to become a sample which in effect consists of two layers having some what different orientations. This effect has never been further explored. The investigation described in the present paper constitutes the beginning of a series of thorough investigations of texture formation in deformed bee single crystals designed to clear up some of the uncertainties which have been discussed. We have chosen a high-purity 2 pet Al-Fe alloy for this investigation. It is known that the allotropic transformation of iron is eliminated by alloying with approximately 1petAl. Such an alloy, being very similar to silicon ferrite, can be heated to the solidus temperature without phase transformation. One reason for choosing A1-Fe instead of Si-Fe for the present investigation is that we have been able to make single crystals of a vacuum-melted high-purity A1-Fe alloy by the strain-anneal method without much difficulty, but were not successful in doing so with a vacuum-melted high-purity Si-Fe alloy. For many research purposes,

Jan 1, 1962

By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957

By C. H. Li, J. A. Sarteli, W. Bonfield

The stress to cause a permanent micros train of 2 x 10-6 in. per in. (defined as the microscopic yield stress) in beryllium is found to be very sensitive to surface condition. The initiation of plastic flow in as-machined specimens, which contain a high density of twins and large residual compressive stresses to a depth of about 0.010 in. from the surface, occurs by the nucleation of slip from high stress fields around twin tips in the surface layers. Removal of the damaged surface layers by chemical polishing results in an appreciable increase in the microscopic yield stress, which is attributed to the remoual of stress raising twins rather than to the release of residual stresses. IT is well known that the macroscopic mechanical properties of beryllium are very sensitive to the nature of its surface finish. Matthews and coworkers1 have shown that the tensile strength of rolled beryllium sheet can be considerably enhanced by chemical polishing, presumably due to the removal of the high concentration of notches, twins, and large residual compressive stresses normally found in the surface layers of ground specimens. There was no similar effect of surface condition on the macroscopic yield stress (the stress to produce 0.2 pct strain), a point to which we shall return. To date there have been no extensive studies on the effect of surface condition on the microstrain region of beryllium. Recent measurements2 of the stress to cause a permanent microstrain of the order of 10-6 in. per in. on machined hot pressed QMV beryllium, gave values ranging from about 600 to 3500 psi. Reasons for the considerable scatter in the results were not discussed. In this paper, we wish to show that the microstrain region of polycrystalline beryllium is, in fact, very sensitive to surface condition. The stress to cause a permanent strain of 2 x 10-6 in. per in. which for convenience we will refer to as the microscopic yield stress, can be increased by almost a factor of 2 by minimizing the amount of surface damage. The variation of microscopic yield stress is attributed to the presence of twins in the surface layers, rather than to residual compressive stresses. EXPERIMENTAL PROCEDURE The starting material for this investigation was commercial purity hot pressed QMV beryllium, with an average grain size of about 20 . The effects of surface treatment were assessed by comparing the microstructure with residual stress measurements and microstrain properties. Specimens were prepared for metallographic examination by wet grinding with 240, 400, and 600 papers, followed by polishing with a suspension of fine alumina in warm 20 pct oxalic acid. After this treatment, the surface could be examined, either in the unetched condition with polarized light, or after etching in 2 pct hydrofluoric or boiling 20 pct oxalic acid with normal light. Thin films of beryllium suitable for electron transmission study were prepared from bulk specimens by chemical polishing with hydrofluoric and phosphoric acids, and were examined in an RCA-EMU-3 electron microscope. Residual stress measurements were made by a procedure similar to that of Treuting and Read.3 Specimens 4.0 in. by 0.625 in. by 0.080 in. were prepared by three different machining procedures, namely: turning, grinding, and sawing, in order to introduce different levels of residual stresses. An electrical resistance strain gage was attached to one side of the specimen, and that surface was then protected by an acid-resistant enamel, while the opposite surface was removed by etching approximately one thousandth of an inch at a time. The change in specimen curvature in the longitudinal direction was noted and the residual stress was calculated by the following formula:

Jan 1, 1963

By W. A. White

UNDERCLAY squeeze is the plastic flowing of underclay below coal pillars into mined-out entries and rooms. Squeezes may be caused either by wet mine conditions where the moisture is taken up by the clay—making it more plastic—or by the presence of certain clay minerals, such as mont-morillonite, which are plastic when there is enough natural moisture. Under either condition, sufficient stress will cause the underclay to flow. Squeezes may fill an entry or room within several hours, or it may be several months before movement stops. Squeeze areas commonly cover hundreds or thousands of square yards. The Coal Div. of the Illinois State Geological Survey has collected samples of underclays from various mines and from cores drilled by coal companies in the state. From these samples natural moisture content, particle size and particle size distribution, and clay mineralogy are determined. Data from samples collected from the underclay below Herrin (No. 6) coal in the Lumaghi Coal Co. mine near Collinsville, Ill., are used in this report to clarify points in the discussion. Data from samples taken from other mines lead to the same conclusions. A generalized geological section for the area is given in Table I. The underclay below coal No. 6 ranges from a few inches to 3 or 4 ft thick. The upper 6 to 18 in. are noncalcareous; the lower part becomes more calcareous with depth. Limestone nodules become larger with depth, almost grading into the limestone below. In areas where the clay is nearly absent the limestone may thicken to take its place; thus they may complement each other in thickness. There are two types of squeeze areas in a mine. In one type up to 3 or 4 ft of underclay lie in what appears to be a depression in the limestone underneath. This is suggested by a rim surrounding the squeeze area where the underclay is thin and the limestone lies within a few inches of the coal. In the second type the underclay of the squeeze area is surrounded by underclay of similar thicknesses which does not squeeze. Test Methods: Natural moisture content, particle size and particle size distribution, and clay mineralogy were determined by the following methods: Natural moisture is the moisture content a clay contains in its natural environment, expressed in percentage of the weight of ovendried clay (110°C or 230°F). To obtain the natural moisture content, given in Table 11, the clay samples were sealed in containers as soon as the samples were taken in the mines. Particle size and particle size distribution were determined by the pipette method,' and the data were plotted as cumulative curves, Fig. 1, on semi-logarithmic paper. Particle size was plotted on the logarithmic scale and percentage on the arithmetic scale. The quartiles (diameters that correspond to frequencies of 25 and 75 pct) and medians (diameters that correspond to the frequency of 50 pct) of the samples were determined from these curves. The clay minerals were identified from the data obtained by differential thermal' and X-ray powder" techniques. The differential thermal analyses were made on the whole samples, whereas the X-ray analyses were made on fractions of less than 2p. Data and Discussion Moisture Content: After the sealed jars had stood for 24 hr, those that contained squeeze samples had perspired, so that droplets of water had accumulated on the insides of the jars. Table II shows the moisture in the clay after it had perspired for 24 hr. (This perspiring was not noted in samples from nonsqueeze areas.) After perspiration one of the squeeze samples still had a higher moisture content than the samples that did not squeeze. Clay Mineralogy: The thermal analysis, Figs. 2 and 3, indicates that the clay minerals are chiefly micaceous in type; the low-temperature endothermal

Jan 1, 1957

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2'3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962

By W. C. Phalen

SALT-MAKING PROCESSES THE production of salt in the United States divides itself at the outset into two distinct classes: (1) The mining of rock salt and its purification and separation into marketable sizes, and (2) the production of salt by evaporation from brines, bitterns, and other solutions. The processes employed at the present time in the manufacture of salt by evaporation may be outlined as follows: 1. Solar evaporation. 2. Direct-heat evaporation (a) in open kettles; (b) in open pans. 3. Steam evaporation, (a) in jacketed kettles, (b) in grainers. 4. Vacuum-pan evaporation. In this paper only the solar-evaporation processes practised in different parts of the United States will be described. SOLAR EVAPORATION Localities In the Eastern States the solar-evaporation process is not generally employed for climatic reasons. In the Western States, particularly in California and Utah, the great bulk of the salt produced originates in the solar-evaporation process. Of the Eastern States producing salt, this process, so far as the writer is aware, is employed in New York State only.

Jan 9, 1914

By Taylor Lyman, E. P. Klier

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.' Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By E. P. Klier, Taylor Lyman

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.' Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By Thomas Wilson

IN a single-crystal cube of iron the arrangement of the atoms is that characteristic of iron at room temperature: the body-centered cubic lattice. X-ray investigation has shown this structure to be characteristic of iron, as it has shown the atomic arrangement of other metals to be characteristic of those metals also. Rarely do substances have more than one characteristic atomic arrangement. Many physical properties of metals are directly connected with their atomic arrangements, so that changes of arrangements produce changes of properties. Only chemical change influences atomic arrangement. If a difference in the physical properties of a metal is caused by a process which involves no chemical change, the cause of the difference in properties must be sought elsewhere than in the atomic arrangement. Frequently this cause can be traced to alteration of crystal orientation. The orientation of a crystal may be defined as the relationship which the crystallographic axes bear to some quantity of reference. A cube of iron appears cubic whether it is regarded from a face, an edge, or a corner. Yet these three positions represent three different orientations of the cube with respect to the observer. It is evident that the orientation of this cube of iron, unlike the atomic arrangement, is not characteristic of iron but is entirely dependent on the previous history of the cube. Most of the processes of metal working, such as wire-drawing, rolling, and bending, change the orientation of the crystals present in the worked metals. These processes usually tend to produce rotation of the crystals into positions approaching a mean. Specimens of metals show-ing this characteristic are said to possess a preferred, orientation. Tensile strength, ductility, and many other properties are influenced by orientation changes; therefore two specimens of the same metal may show different values of these quantities. In metal specimens possessing a narrowly limited preferred orientation, these quantities will vary in magnitude in different directions throughout the specimens. The investigation of the influence of manufacturing operations upon crystal orientation, and hence upon physical properties of metals, is an important

Jan 1, 1929

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By R. H. Hawkins

AN investigation of the applicability of geophysical methods to north-ern Ontario lignite deposits was undertaken early in 1930 by the Ontario Research Foundation at the request of the Ontario Department of Mines TABLE 1.-Formations Associated with Moose River Basin Maximum System Formation Lithology Observed Correlation Thickness, Ft. Pleistocene Marine clays 150 Glacial till (Minimum Interglacial 30) clay and peat Glacial till Lower Cretaceous or Mattagami Fireclay, sand 138 Kootenay (?) Upper Jurassic. and lignite Devonian (Upper) Long Rapids Petroliferous, 50 Portage and black and gray Genesee shale Williams Limestone and 87 Tully (?) Island calcareous shale Devonian (Middle).... Abitibi River Gray fossiliferous 65 Onondaga limestone Devonian (Lower) ?... Moose Rive- Limestone and 50 gypsum Devonian (Loner) Sextant Arkose, clay, etc. 50 Pre-Cambrian Syenite, granite gneiss, etc. Igneous intrusives. . Lamprophyre dikes cut the Abitibi River and lower formations. (Permission of Ontario Dept. of Mines) and was financed in part from a research grant made by the latter organ-ization. The work to date has included gravitational, magnetic and electrical resistivity studies. The gravitational and magnetic measure-

Jan 1, 1933

By Henry Howe

§1. FOUR ASPECTS OF FLOW in the plastic deformation of steel by overstrain, such as punching, wire-drawing, tensile rupture, etc., are: (1) The inter-granular, i.e., the relative movements of the several grains, each as a whole; (2) the intra-granular, i.e., the relative movements of the masses of ferrite or cementite and pearlite within those grains; (3) the intra-pearlitic, i.e., the relative movements of the pearlitic ferrite and cementite; and (4) the crystal unit slipping, i.e., the travel of the minute units past each other, along the slipping planes, giving rise to the slip bands of Ewing and Rosenhain. It may be objected justly that (2), (3), and (4) are in a sense "intra-granular," and that (4) is in a sense "intra-pearlitic." Hence clearness may be gained at times by calling these "Movements of the 2d, 3d, and 4th orders" respectively.

Jan 4, 1914

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By W. D. Sylwestrowicz

In tests on polycrystalline copper and aluminum, the ratio of the yield stress to modulus of elasticity was found to be strongly dependent on tempemture. Also, it was shown that the change of the yield stress with temperature of a material at a given temperature and deformed to a given yield stress, but not necessarily to the same strain, does not depend on previous mechanical thermal history. Likewise, for a material at a given temperature and deformed to a given yield stress, the rate of work hardening is independent of the temperature of prior stressing. It has been shown by Los and Orowan1 and by Dorn, Goldberg, and Tietz2 that the temperature dependence of the yield stress-strain curves of crystalline materials reflects two effects: not only does the yield stress of a material in a given structural state depend on the temperature, but the structural state (and the corresponding strain hardening) after a given amount of plastic straining also depends on the temperature at which the pre-straining has been carried out. Thus, for instance, if a specimen of a ductile metal has been strained along the stress-strain curve 1 at room temperature to point A, Fig. 1, and then the straining continued in liquid nitrogen along curve NR, the yield stress A' immediately after lowering the temperature is lower than the yield stress A" of a specimen that has been strained by the same amount in liquid nitrogen (along curve 3). AA' represents the effect of the temperature change upon the yield stress of the specimen pre-strained at room temperature; A' A" is the excess strain hardening acquired if the pre-straining has been carried out in liquid nitrogen instead of at room temperature. The dependence of the yield stress (i.e., of the structural state acquired during preceding straining) upon the conditions (speed, temperature) of a pre-straining is the reason for the nonexistence of a so-called "mechanical equation of state" for plastic deformation. A 'mechanical equation of state" is a relationship of the form F(s,E, e, T) = 0, or s = f(E, E, T) [1] It was first suggested by Ludwik3 that plastic deformation might obey such an equation; this, however, was conclusively disproved by experiments of Kochendorfer.4 Additional disproofs were given in

Jan 1, 1959

By F. L. Bosqui

INTRODUCTION The history of the development of gold metallurgy in South Africa is divisible into two periods: That preceding the introduction of the cyanide process on a commercial scale in 1890; and the 24 years intervening between that important event and the present time. The period between the discovery of the banket reefs of the Witwatersrand and the year 1890 was one of phenomenally rapid progress in mining development, but of no special interest to the metallurgist. There were no strikingly original or distinctly local advances in the treatment of gold ores. Californian practice in stamp milling and amalgamation prevailed, in mills ranging in equipment between 5 and 50 stamps, operating within a wide range of efficiency, and under the trying conditions usually en¬countered in a new and isolated field. The somewhat incomplete records of gold output of that period show that in December, 1887, there were 20 producing companies in the Witwatersrand district, of which 10 had mills, the largest being of 20 stamps. The only official record of returns for May, 1887, was that of the Wemmer mine, whose modest achievement with a 5-stamp, mill was 100 tons crushed, producing 887 oz. 3 dwt. of gold. This is interesting in view of the .present-day output of this field, which in 1913 reached 8,430,998 oz. The rapid increase of production during this first period (May, 1887, to January, 1891) is shown by the following summary for the year 1890:1 Total tons crushed 702,828 Number of stamps in operation 1,046 Average number of tons crushed per stamp per day 2.36 Yield of gold, ounces 494,817 Yield per ton, pennyweights 13.36 The stamp duty ranged between 1 ½ and 4 tons per day, according to weight of stamp, fineness of screen, and operating skill available. The prevailing weight of stamp was about 900 lb., and the screen, 900 meshes to the square inch.

Jan 5, 1915

By Herbert Clark Hoover, Lou Henry Hoover

PREVIOUSLY I have given much information concerning the miners, also I have discussed the choice of localities for mining, for washing sands, and for evaporating waters; further, I described the method of searching for veins. With such matters I was occupied in the second book; now I come to the third book, which is about veins and stringers, and the seams in the rocks1. The term "vein" is sometimes used to indicate canales in the earth, but very often elsewhere by this name I have described that which may be put in vessels2; I now attach a second significance to these words, for by them I mean to designate any mineral substances which the earth keeps hidden within her own deep receptacles.

Jan 1, 1950

By Hans Lundberg

IN ORDER to comprehend the help and information that may be expected from electrical prospecting, it is necessary to have at least a general knowledge of the methods and principles involved in preparing and interpreting results obtained in the field. Electrical prospecting is rather complicated, both in theory and practice, and in order to make a brief description clear to the practical mining man it has been necessary to idealize and generalize the problems, at the risk of having such simplification criticized by the theoretical man. This simplification must not be misinterpreted as showing a lack of theoretical knowledge. FIG. 1.-FLOW OF CURRENT IN AND AROUND A CONDUCTING BODY. For its operation, electrical prospecting mainly, depends on the fact that most metallic ores conduct an electric current much more readily than barren rocks. If an electric current flows through a block of ground within which a body of chalcopyrite is enclosed in country rock of. schist, the current will find less resistance to its passage through the chalcopyrite than through the schist, even though the passage through the latter be much shorter. This is because the longer path through the chalcopyrite offers less resistance, owing to the superior electrical conductivity of the chalcopyrite (Fig. 1).

Jan 1, 1928

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5'9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1' at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.' It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By M. A. Rigdon, R. E. Grace

The dissociation of cupric oxide to cuprous oxide and oxygen was studied with a microbalmce technique at 700" to 750°C. In this temperature range the dissociation pressure of the reaction 2CuO= Cu2O + 1/2 O2 was: The theory of near-equilibriwm reaction rates predicts a linear relationship between reaction rate and the Gibbs free-energy change for small values of AF/RT. This correlation is found to be valid for AF/RT = -0.1 or approximately 200 cal per mole away from equilibrium. THE theory of reaction rates near equilibrium as developed from classical thermodynamics suggests a small range of linear behavior between the overall reaction rate and the free-energy change accompanying the process. The extent of this linear correlation is generally unknown, even to the order of magnitude. The idea of linearity is also found in the formal mathematics of coupled transport phenomena, e.g., chemical diffusion, thermal diffusion, thermoelectricity, and so forth. The linear array of forces and fluxes which leads to various main and cross coefficients is predicated upon linearity between reaction rates and the bulk thermodynamics which govern the process. The general case in reaction kinetics is well-known: the magnitude of the free-energy change does not cor- relate with observed reaction kinetics, irrespective of whether the process occurs by diffusion or chemical reaction or both. The real need is to investigate specific reaction paths near equilibrium in order to learn of the limitations in attempting to correlate reaction rates and thermodynamics. It is the main purpose of this paper to examine the dissociation kinetics of cupric oxide under conditions of known driving force where the dissociation process is likely to occur by chemical reaction. A secondary objective is to obtain equilibrium data for the CuO-Cu20-O2 system. In a prior paper Edmiston and race' investigated reduction kinetics of wustite in H2-H2O gas mixtures. The present study was carried out in oxygen according to the following reaction:

Jan 1, 1969