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By J. L. Walter

Extra-low carbon iron sheet, when deformed and annealed, undergoes exaggerated or abnormal grain growth in the critically deformed regions of the sheet. This exaggerated pmth occurs, for low strains (3 to 6 pct), only in sheet which has a fine dispersion of precipitates in the subsurface region of the sheet and fewer and coarser precipitates in the sheet interior. These particles have been identified as manganese sulfides. Wing the anneal, grains near the surface are gvowth-inhibited by the fine particles but the grains in the interior are free to grow normally. With the additional driving force provided by the strain energy, the interior grains first grow into the small subsurface pains. Eventually, these growing grains grow completely through the sheet. Calculations of limiting grain sizes at various values of strain indicate that a volume fraction of precipitates in excess of 10-' would be required to eliminate exaggerated growth in material strained to 10 pct. OPEN-COIL annealing has made decarburization of sheet steel both efficient and economically practical. Use of such material for porcelain-enameling stock is one of many possible applications of low-carbon iron since carbon in steel is deleterious to porcelain-enameling properties.' However, the extra-low carbon iron presently available presents another problem, that of exaggerated grain growth in regions where the sheet has been deformed as by bending or stretching. In exaggerated grain growth a few grains start to absorb their neighbors and these may become very much larger than the average grains of the sheet. Other names for exaggerated grain growth are coarsening, critical grain growth, secondary recrystallization, abnormal grain growth, or discontinuous grain growth. While this grain growth does not affect the enameling qualities of the low-carbon iron sheet, their presence results in a marked reduction of tensile-yield strength in the region of the sheet containing the large grains. The loss of tensile yield strength may render the material unsuitable for many applications . This report describes the results of a study undertaken to determine the cause of the exaggerated grab growth in extra-1ow carbon iron and, if possi- ble, to prescribe practical procedures for its prevention. GENERAL THEORY The driving force for exaggerated grain growth is the grain boundary free energy. This driving force is proportional to (l/rl + l/r2) where rl and r2 are the mutually perpendicular radii of curvature of the boundary between the growing grain and the grain being consumed. Thus, the greater the difference in size between the growing grain and the matrix grains, the higher the driving force for grain growth. If, however, the matrix grains are free to grow simultaneously, the driving force for exaggerated growth will be diminished. Stability toward growth of the matrix grains may be caused by a) a strong single orientation texture (texture inhibition),' b) a dispersed second phase,3"5 c) the thickness effect,' or d) intergranular segregation.7"9 As exaggerated growth occurs when growth of the matrix grains has been slowed by the stabilizing processes mentioned above, there must be an additional factor acting to promote growth of a few of the grains to the point where they are enough larger than the matrix grains that boundary energy driving forces are sufficient to cause continued growth. For instance, at the annealing temperature, growth-inhibiting inclusions may slowly dissolve and coalesce. Eventually, a grain boundary becomes unlocked and migration occurs at the expense of neighboring grains. Or, an additional driving force may be supplied to some of the grains if the material is strained. Then, since some grains will be strained less than others, the difference in strain energy between adjacent grains may be sufficient to overcome boundary locking and allow growth of the grains with lower strain energies. In the present study, therefore, such factors as the presence or absence of dispersed phases, the nature of the exaggerated growth, and the effect of strain have been considered. EXPERIMENTAL PROCEDURE I) Material and Processing. Three types of low-carbon iron were used in this study; types A and B were commercial grades, each from a different supplier.* The precise details of the processing of

Jan 1, 1963

By Andrew Roy

THE Mahoning Valley coal region lies on the extreme northern outcrop of the Ohio coal-field, and all the mines, with one exception, are opened on the lower coal of the series, No. 1 of the Ohio Geological Survey. The coal ranges from an inch to five, six, and sometimes seven feet thickness, the workable height being between two and a half and six feet. There are two varieties of coal, known in market as "Briar Hill coal " and " Mineral Ridge coal;" both varieties are drawn from the same seam. The Briar Hill coal is generally called block coal, and is the kind so largely used in a raw state in smelting iron. It pos¬sesses a laminated structure, easily splitting into horizontal sheets, but is very difficult to break in the opposite direction. The faces of the layers are often covered with a soft, dead, carbonaceous material, like charcoal, and the whole seam throughout is marked by alternate layers of dead and bright-looking coal. In the act of combustion the coal neither swells nor changes form, the masses retaining their shapes until they fall to ashes in the furnace. The Mineral Ridge variety is much softer, and is also shorter in the grain than the Briar Hill. kind, and it contains a good deal of

Jan 1, 1876

By C. G. Rhodes, D. Kramer

The kinetics of precipitation of transient a phase during the transformation in U-16 wt pct Mo between 400° and 550°C were studied using quantitative metallography and electrica1 resistiuity measurements. The volume percent of a phase goes through a maximum in time, corresponding to a critical degree of progress of y' formation. prior to its re-solution after prolonged annealing. The fastest rate of a precipitation oc-cuvs at 500°C with a concomittant lowest peak of 9.5 vol pct a. At 450°C, 14 vol pct a, greatest fov any temperature, was observed after 24 hr witlz an associated slowest rate of formation. a precipitation at 400°C ceases after approximately 160 hr and the amount of a present remains unchanged after long times at temperature; no y' was observed metallographically at this temperature. IN the U-Mo system at 16 wt pct Mo, an ordering reaction takes place below 600°C, see Fig. 1, whereupon the random bcc solid solution, y, transforms to the ordered bct phase, y'."2 The new unit cell is constructed of three old unit cells somewhat distorted. While attempting to study the kinetics of this transformation it was observed that an unexpected phase was precipitating out early during the transformation anneal reaching appreciable amounts before disappearing after long times. The y' appeared in the presence of this new phase and after long times constituted the whole sample. Owing to the high optical activity of this unexpected phase under polarized light, it was suspected to be the a phase. Subsequent X-ray powder pictures confirmed this belief. The kinetics of a phase formation and disappearance is the subject of this paper. EXPERIMENTAL PROCEDURE A) Alloy Preparation. Alloys for this study were prepared by vacuum induction melting normal reactor grade uranium and 99.5 wt pct Mo pellets in thoria crucibles. Two ingots were prepared, and sections of the top and bottom of each ingot were chemically analyzed for uranium and molybdenum content. The results of the analyses appear in Table I. B) Metallography. Samples of 16M were wrapped in tantalum foil, sealed in evacuated (5 X 10"6 mm of Hg) quartz capisules, and annealed at 1110"C prior to being transferred directly to the transformation temperature. They were examined metallographically after increasing times to determine the progress of the transformation at 400°, 450°, 500°, and 550°C. The samples were prepared for metallographic examination by mechanical polishing with diamond paste and electrolytic polishing with a solution of glacial acetic acid and chromic acid. Since the y' phase is tetragonal, its presence can be detected by viewing the sample in polarized light. To increase the contrast between y' plates, the samples were electro-etched in a 10 pct oxalic acid solution. To reveal a phase in bright field (it can be seen in polarized light in the "as-polished" state), the samples were electro-etched in a solution of citric acid and nitric acid. To determine the vol pct a phase, a variation of the one dimensional systematic point count method as described by Hilliard and cahn3 was used. The

Jan 1, 1962

By J. E. Burke, Y. G. Shiau

SEVERAL attempts have been made to account for the fact that grains in a fully recrystallized metal will coarsen on annealing Two fundamentally different hypotheses have been advanced; with several variations of each. One school considers that the cause of grain growth is the surface energy of the grain boundary The theory of Jeffries1 that grain size and grain size contrast control growth is an example The second school considers the primary cause to be a difference in the lattice energy on either side of the grain boundary The more perfect grains are considered to grow at the expense of their less perfect neighbors, with a decrease in free energy, and a consequent increase in the stability of the system. Burgers2 presents the case for the strain or lattice imperfection theory of grain growth quite completely The latter theory is attractive, since there is no doubt that differences in lattice energy or lattice perfection can cause grain boundary migration A recrystallization nucleus grows for this reason as was beautifully demonstrated by van Arkel and Ploos van Amstel3 Although it is generally stated that grain growth does not precede recrystallization, several workers4,5 have shown that small strains may induce a single crystal in an aggregate to grow, or at least may cause some' grain boundary migration The origin and nature of the imperfections that are considered to be responsible for normal grain growth have never been clearly described, but it is generally agreed that they are a consequence of the difficulty of atomic reorientation in the solid state, and that they do not seriously differ from the type of imperfection that-can be introduced by mechanical deformation An object of the present work was to determine whether the introduction of mechanical deformation would cause grain growth in a specimen which would not otherwise show it under the conditions used It was also planned to determine the effect of such deformation the rate of growth in a specimen which would show - growth in the unstrained condition Recently Maddigan and Blank6 have indicated that slightly strained specimens of alpha brass can undergo considerable growth prior to recrystallization if annealed at low temperatures French7 has reported that at deformations less than 17 pct it is very difficult to detect the beginning of recrystallization in the same material. It was therefore planned to broaden this work to include a complete study of the microscopic behavior of alpha brass under conditions of temperature, time, grain size and deformation such that recrystallization would not occur or would occur to only a small extent EXPERIMENTAL PROCEDURE The brass was prepared by melting cathode copper and commercially pure zinc

Jan 1, 1947

Selected bibliographies of the Iron Resources of the World and the Coal Resources of the World have' been prepared by the Engineering Societies Library for the National Research Council from the most prominent. American, English and foreign books and periodicals. The bibliograpies are intended as a guide to the literature giving economic

Jan 5, 1919

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..' and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young's modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen's5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By George I. Adams

Peru is divided into three regions—the coast, the ~ierra, or high mountainous region, and the " montaiia," or forest region of the Amazon basin. The Coast.—The coast is an arid region. No rain falls excepting in the extreme northern part, which borders the Gulf of Guayaquil. There is, however, a slight precipitation in the form of mist (gcirua), which occurs on the coast hills during the so-called winter months. The aridity of the coast is due principally to the antarctic, or Humboldt, ocean-current, which, being cold and having a temperature lower than that of the land, absorbs rather than produces vapors. The coast mists occur during the season when the land is relatively cold. N ear the Gulf of Guayaquil the antarctic current diverges from the coast, so that in the Tumbes valley and adjacent country the conditions in the summer months are such as prodnce rains. In the remaining valleys of the coast, agriculture is made possible only by means of irrigation, and is accordingly very limited in extent, although rich and varied. In the northern and south-central portions of the coast, plains extend inland from the sea, while in the southern part there is a coastal plain separated from the Pacific by a range of coast hills. Between the northern and south-central plains, as well as between the south-central and southern, the foothills of the sierra descend to the seacoast. The Sierra.—The sierra embraces the high land dominated by the lofty cordilleras of the Andes. In the southern part of Peru there are two cordilleras, the western and the eastern, which enter from Chile and Bolivia respectively, and inclose between them the Titicaca Lake basin. To the north of Lake Titicaca these cordilleras unite in the knot of Vilcanota, south of Cuzco. From this knot three cordilleras, known as the western, the central, and the eastern, extend to the northward, reuniting in the

Jan 1, 1909

By Carl F. Floe, Hung Liang, Michael B. Bever

DATA on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Sims1 have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan,2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett6 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid - iron were reported in 1910-1911 by Sieverts and Krumbhaar8 and by Sieverts.9 They found that 100 grams of iron absorbs 28 C.C. of hydrogen at 1550°C. and one atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 c.c. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon

Jan 1, 1946

SIR ROBERT HADFIELD, London, England (written discussion*).-We have in the past known so little about tungsten that an important paper such as Mr. Zay Jeffries contributes is most welcome. I have not much personal knowledge on the subject except as regards combinations of iron with tungsten. I put forward the results of my research on natural alloys in 1903,1 and so far as I know the facts there presented still stand. Singular to say, tungsten added to iron affects the electrical resistance less than any other added element. The following tables taken from research work by myself and Sir William Barrett may be of interest.

Jan 10, 1918

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 mil- lion tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms.

Jan 1, 1954

By J. Suiter, H. F. Ryan

H. F. Ryan and J. Suiter (CSIRO)—In this paper the authors have presented "a physical model which has as its central hypothesis the solution strengthening of regions along grain boundaries in the order of tens of angstroms thick", and their calculations have used 40Å as the zhalf-width of this boundary region. Selection of this value by the authors suggests that they were unaware of a number of recent field-ion microscope observations of grain boundary structures (e.g., Refs. 29 and 30). The accompanying figure, Fig. 9, shows a portion of an ion micrograph of a tungsten specimen containing a grain boundary, and the regular arrangement of atoms in various crystal planes in each grain can be seen, except in the boundary zone which is not more than two atom diameters in width. Since it is expected that solute atoms will segregate only to the region where the lattice is disturbed, it would seem that a value of 4Å for the half-width of the boundary region would be more appropriate than the value of 40Å assumed by the authors. If the former value is used in Eq. [8] of their paper to obtain curves showing solute concentration in the grain boundary as a function of temperature, the resulting curves differ significantly from those obtained by the authors. Although there are only relatively slight changes in the regions corresponding to higher temperatures (i.e., grain boundary concentrations of approximately 1 at. pet), at lower temperatures the curves are no longer realistic. For example, the curve corresponding to u = 7000 cal per mole gives a solute grain boundary concentration in excess of 100 pet at a temperature of approximately 360°K, and "flattens out" at a grain boundary concentration of about 300 pet! Similar results are obtained with each of the other curves. Ion microscopy of dilute solid-solution alloys has shown that solute atoms give rise to image points which in most cases are of higher intensity than those of the solvent atoms.31 If the same behavior occurs when the solute atoms are present in much lower concentrations then ion microscopy should provide a sensitive tool for studying the segregation of impurities to the grain boundary regions. Although many grain boundaries in tungsten have been examined after different thermal and mechanical treatments, there has not been, as yet, any systematic study of such segregation. In general the micrographs show no clear indications of marked grain boundary segregation, but occasionally areas are found where the grain boundary contains an appreciable number of image points of high intensity in a very narrow zone, see Fig. 9. If it is assumed that these correspond to impurity atoms then it is possible to estimate the impurity concentration both in the grain boundary and within the body of the grains. Application of this method (to a larger area

Jan 1, 1965

By P. H. Mell

The little village, from which this formation receives its name, is situated on a bluff of the Alabama River, 175 feet above water level. This bluff is a portion of high table land that begins in the western portion of Choctaw and extends through Clarke and Monroe counties. We find points on this ridge more than 100 feet higher than Tuscaloosa, and nearly as high as the Tennessee River at Tuscumbia. Through this the Alabama River cuts its way, exposing a beautiful cross-section of the strata, of which the accompanying sketch may give some idea. The fossils are found about 75 feet below the surface and 100 feet above the level of the river. There are seven distinct strata. 1. The lowest, extending from the water's edge up the bluff 80 feet, is a soft calcareous rock containing about 15 per cent. of carbonate of lime, with occasional specks of mica. In this a few Ostrea, Turritellæ, and Flustræ were found, but so friable as to fall to pieces when handled. 2. Next comes a stratum varying from 2 to 8 feet, consisting of

Jan 1, 1880

By H. Q. Golder

With the development of open-pit mines of ever increasing depth, the stability of the pit slopes in soil and rock is of growing economic importance. How is it, considering the newness of the problem that we know anything at all about the stability of man-made slopes? How much do we know and how did it all begin? We can make a reasonable estimate of the stability of a slope in soil, but we know as yet woefully little about slopes in rock because the problem is much more complex. It is only with the development of the capacity of the computer to handle wearisome calculations that any but the simplest of stability problems in rock have become possible of solution. But what we do know is a guide of immense value in the design of slopes in rock. But remember that the computer is a great elevator; it takes everyone's feet off the ground! So our study began with soils and what is now known as "Soil Mechanics", which is a translation of the German term "Bodenmechanik". It is a pity that the title of Terzaghi's book "Erdbaumechanik" was not used instead. But here the task of the translator is difficult because English lacks the facility of German to string together several words and make a new one whose meaning is unequivocal. Thus, we have the three German words 'Erde' 'Bau' and 'Mechanik'. 'Erde' means "earth" in almost all the English senses including "soil". 'Bau' and 'bauen' convey the meaning of building and construction, and 'Mechanik' means "mechanics" which includes statics and dynamics and the 'mechanics of materials', etc. So that a correct translation of the German is a phrase like "the mechanics of construction with, in or on, earth or soil." However we are stuck with 'Soil Mechanics' and that is where it all began. Now this study or subject did not begin with 'Terzaghi' although his contribution to the subject is unquestionably greater than that of any other single person. Every scientific discipline has its 'classical problem' and that of soil mechanics is 'the earth pressure problem' and it began in the 17th century. In fact, it probably began before this with the introduction of gunpowder to Western Europe in about the 15th century, but the first known reference to the problem was by Vauban, a distinguished French military engineer who lived from 1633 to 1707 and who gave rules for the dimensions of retaining walls from 6 to 80 ft. in height. The soil properties were not mentioned by Vauban probably because the rules were intended to be applied to fortifications only, but Poncelet (1840) claimed that Vauban's rules were based on a theory, and not simply on military and practical

Jan 1, 1972

By W. R. Toeplitz

Probably a more descriptive title would be "Much Ado About Nothing." By "nothing," of course, I refer to the porosity which is the main feature of this type of bearing. Porosity has a decided effect on the manufacturing techniques, the structure and physical properties, the oil content, and on the installation and service of oil-retaining porous bronze bearings. A simple curve can be drawn by plotting specific gravity along the abscissa and percentage of porosity by volume on the ordinate. A bronze composition, analyzing 89 Per cent copper, 9.75 Per cent tin, and 1.25 per cent graphite, has an absolute solid specific gravity of 8.5. At this specific gravity, of course, occurs the point of zero porosity. Conversely, at loo per cent porosity, the specific gravity is zero. A similar curve can be drawn for bearings impregnated with oil; the only change being that the specific gravity at loo per cent oil will be 0.89 if we assume that that is the specific gravity of the lubricant. The curve is useful in determining the oil content by volume for any specific gravity. The normal range of oil content for porous bronze bearings of this composition is from 35 to 16 per cent, which is in the specific gravity range of from 5.8 to 7.3. In addition to the amount of porosity, the type of porosity is important. The first consideration here is that the porosity must be intercommunicating. This can be determined by a number of simple tests. The first method, which is very accurate, is to extract the oil in the bearing by cycling

Jan 1, 1945

By Charles W. Goodale

The attention of the Institute has been called by Prof. John A. Church* and Mr. W. Lawrence Austin? to the free-milling ores of the Tombstone mines and their treatment, but the silver-bearing man ganese ores of the district have received only a passing notice. As these ores show some interesting peculiarities, and have yielded not less than 750,000 ounces of silver, they are worthy of some study. The Knoxville, Lucky Cuss, Luck Sure, and Wedge mines (named in the order of their importance) are situated along the northern border of the district. They have been the leading producers of this manganese ore, and possess the same general characteristics. Special attention will be given to the Knoxville, as it has been the one most extensively developed. The limestone belt, in which the Knoxville ore bodies occur, has an easterly and westerly trend, is about 1680 feet wide, and rests on granite on the north, the plane of contact being nearly vertical. It is overlain by quartzite, the contact-plane having a dip of 82°. Some mining has been done along these contacts, and a considerable amount of pay ore has been extracted, but development has been very superficial. The ore found along these contact planes contains very little manganese, and differs entirely from the ore in the lime stones. No attempt will he made to assign this limestone country-rock to a particular geological horizon, as no fossils have been found in it. Prof. Blake, in a paper on "The Geology and Veins of Tombstone, Arizona" (Trans., x., 334), speaks of the middle and upper strati-

Jan 1, 1889

By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,' It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle's publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By R. C. Patterson

In view of the circumstance that very few important changes have been made within the last 15 or 20 years in the equipment of rod and wire mills, the description of a new process introduced by Grenville Mellen, of LleweIIyn Park, N. J., to take the place of the present laborious system of producing rods of lead, zinc, brass, copper, aluminum, etc., may be interesting to members of the Institute. This new process consists in the production of cast rods at one operation in a small continuous casting machine. The hot liquid metal is transferred from the melting crucibles directly into an endless chain of mold blocks in the machine, where solidification takes place, and the rod comes out continuously in a solid form at one end as long as the molten metal is supplied. The operation of these mold blocks so as to produce a solid rod of uniform structure constitutes an important part of Mr. Mellen's invention. The machine (Figs. 1 and 2), 12 ft. in height over all, 2 by 3 ft. in horizontal cross-sectional area, and 6,000 Ib. in weight, has a framework of cast iron, holding in position two endless chains of mold blocks, which are made in sections and join in center alignment. The mold orifice is made up of these mold sections, into which the liquid metal flows. The molding chains are composed of steel blocks, grooved on one face to form the molding cavity, and linked together with flexible joints. Each block is carried on four rollers which guide the chain around the end sprockets and carry it in its course through the machine. The accuracy of alignment requisite to the production of a perfect rod in the mold groove formed by these sections is secured by careful machine work, and by building the four ways, down which the alignment takes place, so that two of the sides are fixed permanently, whiIe the opposite sides are held to their position by spring pressure. The guides carrying the molds, while in casting position, are water-cooled square tubes. The length of this machine is somewhat indeterminate. A certain amount of both time and cooling surface is required to solidify the metal jn the mold; and one may either use a long molding chain and run it fast, or a shorter chain and run it correspondingly slower. We have found,

Jan 1, 1916

By H. W. Paxton, G. M. Pound

A method is outlined for taking into account variation in chemical potential of both components in evaluating capillary effects at growing interfaces. The results are compared with experiment, and seem to be in reasonably good accord for Widman-statten ferrite growing in austenite. ENERY pointed out that during the steady-state growth of phases with a rather small radius of curvature at their advancing edge capillarity cannot be neglected. By proper application of the Laplace equation a correction must be made to the activity gradients down which diffusion occurs. Subsequent workers have concerned themselves with attempts to evaluate specific cases by the use and modification of the principles laid down by Zener.2-5 To solve the problem in its simplest form it is necessary to assume thermodynamic equilibrium at the interface and to select some criterion which will allocate the available free energy between reversible and irreversible processes. Zener chose to assume that the division should be made such that the new phase grew at the maximum rate. Other workers have used the same2,3 or different assumptions, e.g., maximum rate of free-energy dissipation,4 minimum rate of entropy production.5 Li6 has proposed that the "thermokinetic potential" should be a minimum at steady state. The purpose of this presentation is to note that most prior treatments have considered variations due to capillarity only in the chemical potential of the mobile constituent, and that a more consistent treatment must involve a consideration of the variation of chemical potentials of both solute -and sol- vent in a binary system.* As an example, the way in which this arises for ferrite growing from austenite may be illustrated by reference to Fig. l(a). The line OABC shows a typical variation of carbon activity with composition at one atmosphere pressure (at a transformation temperature below A3). In the tip of a growing ferrite plate with a hemi-cylindricab leading edge of radius ?, the pressure due to capillarity is*

Jan 1, 1963

By P. G. Coombs

The kinetics of the cyclic oxidation and reduction processes for palladium powder were examined in the temperature range 848 to 923 K. The changes in oxidation behavior due to cycling are shown to result from the decrease in surface area. Sintering is found to occur only during the reduction process. Oxidation kinetics were found to follow a cubic law with time and yield a relation for the oxidation rate constant of k x = (1.05) 106 exp P74.0). 103 / RT] The kinetics of reduction are demonstrated to be first-order with the rate constant described by the expression: kr = (7.69) 1012 exp [-(208.0) 103 / RT] . In both expressions R is in J.mo1-1.K-1.

Jan 1, 1984

By Maximo Monte-Flores

A PERUSAL of the most recent literature on the subject of hydrocarbons reveals that one point seems, to have been neglected by the various theories; that is, the influence of the bed-rock on the accumulation and distribution of oil and gas. This can be seen from the following statement of the principles of the most accepted theories. ANTICLINAL THEORY The anticlinal theory claims that the accumulation of the hydro-carbons in deposits of commercial importance was brought about by the gravity of the hydrocarbons, the oil and gas being forced to the top of the porous stratum by the difference of the specific gravity of the hydro-carbons and the water. The principal factors toward the accumulation were the general stratigraphic condition of the rocks, their texture and porosity, and their water content. This theory advocated the preexistence of structural deformation as the basis of the motion of gravity, thus implying the principle that the forces that have caused the deformation have had no influence on the movement of the hydrocarbons. STRUCTURAL THEORY According to the structural theory, the accumulation is due, chiefly, to the structure of the subsurface rocks and differs from the anticlinal theory, mainly, in not considering that the motion of the liquids have been caused by the force of gravity.

Jan 1, 1920