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By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.'-' It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer' has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By A. V. Bradshaw, R. I. L. Guthrie

The behavior of large bubbles in the size range 4 to 25 cm3, rising through molten silver, has been studied. It was found that rising velocities were equivalent to those in aqueous systems of low viscosity. Mass transfer coefficients for oxygen bubbles dissolving in silver were found to be 0.036 ± 0.007 cm sec-1, being close to those predicted for transfer through the front surface of the spherical cap bubble only. It is suggested that the surface active nature of oxygen in silver could account for the relatively low coefficients obtained. MANY metallurgical processes involve interactions between gas bubbles and liquids. Examples include the removal of carbon monoxide in Open Hearth Steelmak-ing, the removal of sulfur by blowing air through copper matte during converting, and the removal of hydrogen from steel during vacuum degassing or inert gas flushing. The steps involved in such refining processes include; transport of the dissolved species to the bubble interface, adsorption and chemical reaction of the species at the interface, desorption of product molecules from the interface, and transport of product gas into the bulk gas phase of the bubble. It has been concluded1 that all the interfacial steps involved proceed so rapidly at steelmaking temperatures that transport of the solutes, present in the metal, become the important rate controlling factors provided nucleation phenomena are not restrictive. The O-Ag system was chosen for the investigation into gas bubble-molten metal interactions due to the relatively high solubility of oxygen that enables rates of oxygen transfer to be measured from changes in bubble volume. Other advantages of this system include the absence of a stable oxide phase at an oxygen pressure of 1 atm and the relatively low melting point of the metal which permits the use of a metallic container, providing that it is resistant to oxidation. In those metallurgical processes where bubbles have an important influence, bubble volumes are usually greater than 5 cm3. For this reason the present study relates specifically to single large bubbles of oxygen rising in silver. These bubbles adopt the characteristic spherical cap shape similar to that shown in Fig. 1 for a 30 cc bubble rising in water. After an initial investigation to determine the velocities of inert (nitrogen) bubbles rising in molten silver, experiments were carried out with oxygen and the rates of mass transfer between the oxygen bubbles and the silver were measured. EXPERIMENTAL Apparatus. The apparatus, Fig. 2, for containing molten silver, was constructed from "Nimonic 75" Alloy (75 pet Ni, 20 pet Cr, 5 pet Fe, Mn) and provided for the release of single bubbles from an hemispherical cup, situated at the bottom of the column. The cup was turned by translating the rotation of the drive shaft through 90 deg. This was accomplished by the use of a bevelled gear system, and a smooth drive was provided by the lubricating action of the silver on the gears. Since reliable high temperature seals at 1000°C were found to be impracticable, the filling and drive shaft tubes were extended outside the 3.5 kw resistance wire tube furnace, where connections were made using easily accessible O-ring seals. The apparatus remained gas tight to the atmosphere at pressure differentials far in excess of those used. The filling tube was connected via a small bore tube to the differential pressure transducer. Gas could be bubbled into the inverted cup from two i-in. tubes which passed down the inside of the column to preheat the gas. The temperature of the silver was maintained at 1020°C during all experiments. Measurement of Bubble Volume. In order to calculate mass transfer rates, it was necessary to obtain a continuous record of the bubble's volume during its passage through the column of molten silver. The method adopted for measuring the bubble volume involved closing off the top gas space to the atmosphere prior to each experiment, and recording the variation in gage pressure of this space during the formation and rise of the bubble. Since any change in bubble volume results in an equal change in top space volume, Boyles Gas Law may be applied (for isothermal con-

Jan 1, 1970

By A. H. Bell

The results of repressuring (or gas-drive) have been very encouraging to the several companies doing experimental work along these lines in California. The most notable examples are the Shell and the Union Oil companies at Dominguez, the Marland Oil Co. at Seal Beach, and the California Petroleum Corpn. at South Mountain. The results of the Marland test at Seal Beach are interesting in that re pressuring was started while several wells were still flowing; also, on account of the high pressures required to overcome the hydrostatic pressure exerted by high-head edge water. The well first chosen for repressuring is about halfway up the flank of the structure and had been on the beam making about 250 bbl. of fluid daily, cutting about 60 per cent. emulsion. The fluid lcvel was 230 ft. from the surface and the top of the sand was 4393 ft. Tubing was run to 4000 ft. with a packer and the space above the packer was filled with water to balance the high pressures. Gas was started in slowly to allow the fluid to be pushed back into the sand, and required three days at a pressure of 1500 Ib. per sq. in. before starting into formation. The pressure was once built up to 1800 Ib. and the compressor was shut down for a few hours. When again started, the well took gas at 1500 Ib., and after about three weeks the pressure was dropped to 1450 Ib. The present pressures required range between 1400 and 1450 lb. Volumes as high as 1,500,000 cu. ft. per 24 hr. were put into the well. Increases as high as 50 per cent. in production were obtained in wells up-structure with very little increase in wells down-structure. Also, the water cut on one edge well materially decreased. After about 40 days the repressuring was moved to two wells farther down-structure and the well originally repressured was put on production. The result of this was a great increase in the production of wells one location farther down-structure, a rapid increase in one well one location up-structure, and a decrease in production of the wells farthest up-structure. Later the gas started to short-cut to the nearest well down-structure, nullifying to a certain extent the effects of the repressuring work. The increased production that could be definitely attributed to the repressuring work

Jan 1, 1928

By L. A. Tarshis, H. E. Cline

A stability criterion for a lamellar eutectic interface was derived previously1 assuming that the wavelength, A,. of the perturbation which grows most rapidly is much larger than the lamellar spacing. A. This assumption was required to permit averaging of both the interface temperature and composition over the complicated geometry of a lamellae. If this assumption is invalid, as has been suggested.2,3 then the problem becomes too complicated to solve completely. The first of these analyses1 did not calculate the wavelength. A,. of the initially unstable perturbation. whereas the more recent analysis.' which led to a contradiction of this assumption. did not include one of the key factors for determining this wavelength. To rigorously determine the wavelength, the effect of the curvature of the perturbed interface (not considered by either of the above treatments) must be included. By omitting this term, one would be led to an incorrect conclusion regarding the magnitude of A,. but to an accurate criterion for stability as evidenced by the excellent agreement with experimental observations.' In the case of single-phase alloys. the critical wavelength. A,. for instability can be calculated from the Mullins and Sekerka4 (M.S.) analysis which includes the effects of capillarity. In the following discussion, the M.S. analysis is applied to lamellar eutectics and the critical wavelengths calculated for reasonable growth conditions in Pb-Sn eutectic alloys. In order to apply the M.S. analysis to eutectics. one may substitute i) the effective liquidus slope.1 m*. for the single-phase liquidus slope and ii) the ratio of the bulk alloy composition. C,. to the average interface composition in the liquid (Ci = CE where CE is the equilibrium eutectic composition) for the distribution coefficient to give:

Jan 1, 1970

By Julian Kennedy

When it was decided to erect these furnaces the company also decided to use the Cowper type of stoves. It was, however, desirable to improve upon the plan of the stoves then in operation, to avoid, if possible, some defects which had shown themselves in them. The stoves now in use at Furnaces " A," " B," and " C " are of the well-known type of Cowper stove, having a circular combustionchamber placed at one side of the stove, and a regencrator with crescent-shaped section, resting at the bottom oil cast-iron glatings, which are supported in turn by cast-iron girders, the products of combustion passing up the chamber, down through the flues of the regenerator, and thence to the chimney. The objection to this shape of stove, that the gases would not pass down the parts of regenerator lying beside and behind the combustion-chamber—the horns of the crescent, as it were,—did not apply to the newer form of stoves, with combustion-chamber having a straight wall next to the regenerator; but. there were other defects, the principal ones bring the small size of the openings through the regenerator and the material used for supporting it. The small passages (4" X 4") soon choked up, and when a part of them became entirely closed, not only was the effective heating surface greatly diminished, but as the remaining opening were not sufficient to absorb the heat

Jan 1, 1882

By John T. Norton

In spite of the very general errlployment of nitride hardening, there is still considerable doubt as to the real nature of the mechanism involved. Experience has shown that the addition of small amounts of hardening elements to iron or steel results in a wide variety of desirable properties in a nitrided case. Perhaps the foremost of these elements is aluminum and in this investigation an attempt has been made to study the behavior of aluminum during the hardening process. It is believed that the establishment of a complete atomic picture of the metal at various stages of the process will indicate the relationships between the several kinds of atoms and their individual influences on the physical properties in a clear and direct fashion. A consideration of the problem suggests a surprising similarity between the mechanisms of nitride hardening and of age-hardening. It is now generally understood that age-hardening may take place by one of two distinct processes, the first involving the precipitation of a finely dispersed phase and the other being concerned with the modification of an existing phase. Following much the same line of reasoning, two theories of nitride hardening have been suggested. The first explanation, which has been generally discussed, particularly by Fry,' states in brief that the presence of aluminum causes the precipitation of aluminum nitride during nitriding and that this finely dispersed phase is the primary cause of hardening. The second explanation, which has not been published but which has been freely discussed by those interested in the problem, postulates the substitution of aluminum atoms for certain of the iron atoms in the several iron-nitrogen phases in the same manner that the substitutional iron-alurninurn solid solution is formed. The marked increase in hardness, as compared with the aluminum-free system, is attributed to the severe lattice distortion accompanying this replacement.

Jan 1, 1934

By T. C. Desollar

The group of iron-ore mines known as the Red Ore Mines, owned and operated by the Woodward Iron Co., is on Red Mountain approximately ten miles southwest of Birmingham, Ala. At the present time NO. 1 and No. 3 mines are active, No. 2 mines having been abandoned in 1928. Ore from this group of mines was first mined in 1882, and originally came from open cuts along the outcrop, but, when the "soft ore" (weathered hematite) was mined out and the harder ore was encountered, it became necessary to develop the orebody by means of slopes driven in the ore formation. The three mines to date have produced more than 22,000,000 tons, and the two operating mines now have a capacity of over 1,000,000 tons per year. Geology The U. S. Geological Survey has described the features of the district. It places the hematite of Red Mountain, commonly called "red ore," in the Clinton formation of the Silurian system. This formation varies from 200 to 300 ft. in thickness, and is composed largely of shale (slate) and sandstone. There are four iron orebeds in the formation, known as the Hickory Nut, Ida, Big Seam and the Irondale seams. The strike of the orebeds is northeast and southwest, and the dip is southeast, the outcrops being on the west side of the mountain. The two seams that have been worked at the Red Ore mines are the Big Seam and the Ida. The Big Seam, which is and has been the principal source of the ore mined, is approximately 20 ft. thick and consists of hematite and ferruginous bands of sandstone. It is separated into "upper" and "lower bench" ore by a slate parting that is about 30 in. thick. All present mining is confined to the "upper bench" ore, which is uniform in texture and drills and breaks fairly easily when the holes are placed so as to take full advantage of the face of the ore. Typical analyses are shown in Table 1. The presence of two water-bearing formations, the Fort Payne chert and the Hartselle sandstone, lying respectively 160 and 300 ft. above the Big Seam, make it essential that in mining the ore any movement of

Jan 1, 1934

By Laurence C. Hicks

Consideration of the past work on the subject of the diffusion of chromium into iron suggested that additional information might be given by the use of X-ray spectroscopy in following the concentration changes through the diffusion zone. Grube and Fleischbeinl packed rods of electrolytic iron in a mixture of alumina and chromium. These specimens were heated in an atmosphere of purified hydrogen for varying lengths of time. After treatment the specimens were examined metallographically and showed the usual structure, consisting of a border of radially oriented columnar grains ending in a sharp boundary line. Reference is made to the fact that etching with certain reagents will attack only the material inside the border of columnar growth and also to the fact that polishing seems to develop a ridge at the position of the boundary between the etched and unetched areas. By chemical analysis of thin layers turned off on a precision lathe, the authors were able to obtain depth-concentration curves. These curves, reproduced in Fig. 1, show that in most cases a pronounced change of slope occurs, corresponding to the position of the boundary of the columnar grains. In a laler paper Grube extends his work to other systems which show the same characteristics.~ He concludes that the reason for the break in the curve is that a hindrance of diffusion occurs at the place where the regularly oriented grains of the diffusion zone meet the random grains of the interior portion, on the assumption that the diffusion velocity in one direction in a grain may be greater than in another direction, and that the grains in the diffusion zone orient themselves so as to give the maximum diffusion rate. Kel1ey" points out that Grube has failed to note that the boundary line does not consistently cross all grains and

Jan 1, 1934

By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

I. INTRODUCTION. LIME-ROASTING is a term proposed by Ingalls 1 for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If, finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse undecomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale, the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the .bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1907

By David A. Sterling, Roger C. Malan

The Atomic Energy Commission is investigating the distribution of uranium and thorium in the Precambrian of the western United States and the relationship of time-space-facies patterns of uranium and thorium enrichment in the Precambrian, to the major resources of umanium in Mesozoic and Cenozoic continental clastic sediments. The results of preliminary studies in the southwestern. United States are summarized. Approximately 50% of the uranium resource of the Free World is in deposits of Precambrian age, principally in lower Proterozoic conglomerates in Canada and South Africa (Uranium Resources, Joint Report, ENEA and IAEA, 1967). Most of the uranium resource of the United States is in Mesozoic and Cenozoic continental clastic sedimentary rocks that fill intracratonic basins. The Atomic Energy Commission (AEC) is investigating the distribution of uranium and thorium in the Precambrian of the western United States and the relationship of time-space-facies patterns of uranium and thorium enrichment in the Precambrian to the major resources of uranium in the Mesozoic and Ce-nozoic host sedimentary rocks. This paper summarizes the results of preliminary studies of the Precambrian in the southwestern United States including New Mexico, Arizona, southern Nevada, and southern California (Fig. 1). The host rock provenances for the major uranium resources in epigenetic deposits of Mesozoic and Ce-nozoic age in the western United States were in areas of extensive Precambrian exposure along the eastern margin of the Phanerozoic geosynclinal belt (Fig. 2). Mesozoic continental clastic sediments in the Colorado Plateau contain about two-thirds of the uranium resource of the United States. These sediments formed from detritus derived from the Mogollon highland in the southwestern United States where the Precambrian was extensively exposed1-1 (Fig. 2). A genetic relationship may exist between this provenance and the major uranium deposits of the Colorado Plateau. The Pre- cambrian might be equally important in the genesis of uranium deposits whether the most important process in the formation of these deposits was the leaching of low-order intrinsic amounts of uranium from Precam-brian granite or from Mesozoic pyroclastics derived from syntexis of the Precambrian basement rocks.' Precambrian Geochronology of the Southwestern United States The Precambrian geochronology of the southwestern United States is in an early stage of systematic study. Until recently, the only basis of correlation was through inconclusive field relationships. However, with the increased use of isotopic age dating, new data are becoming available for correlating regional and local events. As yet, there is no undisputed evidence of ages greater than 1.8 billion years (by) old in the southwestern United States. However, most geologists who have studied the region agree that volcanism and marine sedimentation of predominately eugeosynclinal facies took place in a northeasterly trending geosyn-cline prior to 1.7 by."' Because of insufficient evidence for a pregeosynclinal continental crust, some researchers believe the geosyncline may have developed on oceanic crust.' However, sediments metamorphosed to 1.7 by-old felsic paragneisses in the Panamint Range, California," and southeastward into southern Nevada are believed to have had a nearby continental provenance. The three Precambrian disturbances that are recognized in the southwestern United States are 1.6 to 1.8 by, about 1.4 by, and about 1.1 by-old (Fig. 3). In addition to plutonism, these disturbances are characterized by predominately lower-grade metamorphism. In this report, lower-grade metamorphic rocks include argillite, phyllite, slate, mica schist, and gneiss with relic sedimentary textures. Higher-grade metamorphic rocks, in this report, are recrystallized beyond megascopic recognition of the original rock type. Principal

Jan 1, 1971

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.' It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)'/2af.]' [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954

By John G. Hall

The pumping operations at the Chief mine have been unique in the respect that for many years the entire flow of water into the mine has been disposed of by pumping into natural underground "caverns" or "sinks." Volumes up to 4000 gpm have been pumped into these caverns with no apparent tendency for the caverns to fill with water, and it has never been proven that any of the water returns to the mine workings. Major pumping operations have been carried on during two periods, the first from 1918 to 1927, and the second from 1942 to the present time. Early Pumping Operations CHIEF MINE The Chief Consolidated Mining Co. was organized in 1909, and for the following nine years ore was developed and mined from the 600 level down to the 1800 level, all above the permanent water table, the 1820 level. The ore occurs as extremely-irregular pipes of replacement ore in limestone, and to date a total of approximately 2 1/2 million tons of ore has been produced. The ore was highly oxidized down to the permanent water level, and some highly-oxidized ore runs occur beneath the permanent water table. In 1916, with extensive mining being done on the 1800 level, 20 ft above the water table, there were indications that a zone of secondary enrichment might exist below the water, and in order to follow the ore runs to greater depth, it was realized that arrangements would have to be Made to pump water to the surface. The original pumping installation was designed to pump 350 gpm in five stages against a 1900-ft head to the surface. By January 1919, the water had been lowered to the 1900 level and an excellent grade of silver-lead ore was being produced from the zone of secondary enrichment. At this point. the flow of water equalled the capacity of the pumps, and pumps of an additional 1000 gpln were installed to supplement the original system. By January 1920, the water had been lowered approximately 100 ft, and the total flow of water was 1000 gpm. The water was being pumped from many different places in the mine where ore was being followed downward, with 27 different pumps operating below the 1800 level, mainly Cameron air-driven sinker pumps. These first sinking pumps were cumbersome and inefficient, and each of the larger pumps weighed approximately three tons and required tremeridous volumes of compressed air. During this period, an exploration drift being extended north and west from the Chief shaft on the 1600 level encountered a large natural cavern some 2000 ft from the shaft. This cavern in places measured 60 ft in diameter. Sometime later the disposing of water into this cavern was suggested, and as an experiment to determine the results of such an operation, an attempt was Made to fill the cavern by pumping in a small volume of water, but the water disappeared as fast as it was discharged into the cavern. It was decided then to try the cavern as a drainage outlet for the entire volume of water being pumped to the surface, and the water apparently did not return to the mine workings. Subsequently water up to 3000 gpm was pumped into this cavern. An attempt was made to determine whether any water was being returned from the cavern to the lower workings, and 100 lb of sodium fluorescein salt was added to the water discharged into the cavern, but no trace of it was found in the drainage water in the mine. Results of another such test will be described later.

Jan 1, 1950

By Berke L. Thompson

INTRODUCTION Purpose of Wall System There were 2379.88 m (meters) of tied back wall along Interstate 77 in the Capitol Complex area in Charleston, West Virginia. The main purposes of this wall system was for aesthetics, reduction of excavation, saving the forested slopes, and control of sloughage of the back slopes onto the Interstate. Failure At 1 PM on Thanksgiving Day, 1982, 3 wall panels fell from the insitu position onto the interstate in a matter of seconds. See Fig. 1. The total length of wall that fell was 29.25m. The height of the three panels varied from 10.06m to 10.36~1 and each individual panel had a length along the highway of 9.75m. These were abutting panels that were approximately in the middle of a section of wall 165.81m long. The panels separated from the remainder of the wall at 2 expansion joints that occur at the ends of every 3rd panel. The reinforced portland cement concrete panels were designed on a 76.2mm (millimeter) batter. See Fig. 2 for Wall Dimensions. The footer for these panels was lm wide, was keyed into sandstone bedrock 0.30m and was approximately 1.52m below the portland cement concrete pavement and shoulder. Thirteen of the 17 panels in this section of wall were tied to the sandstone bedrock behind the wall by either 25.4mm or 34.93mm hollow rock bolts. Two panels on each end of the wall were cantilever type walls. The panels that failed had 25.4m hollow rock bolts. A portion of each panel adjacent to both sides of the failure was pulled out from the rock face and appeared to be in imminent danger of also failing. All of the 21 rock bolts in the panels that fell were separated either at the backface of the wall, in the extension from the wall to the rock face or at the rock face. None of the rock bolts had been pulled out of the bond length in the sandstone bedrock. After considering the condition of the wall and

Jan 1, 1984

By R. B. Walker, R. Palmer, L. C. Bryner

The purpose of this investigation was to further study some of the factors affecting the air oxidation of sulfide minerals. Data obtained from laboratory studies on the effect of temperature, concentration of iron salts, pH, and other catalysts on the biological and nonbiological oxidation of sulfide minerals are presented. The oxidation of copper sulfide minerals and subsequent leaching of the soluble copper has long been a profitable operation. The chief oxidizing agent is oxygen from the air. This reaction is influenced by a number of different factors such as temperature, light, hydrogen ion concentration, oxidizing agents, and various catalysts. Sullivan1 found that copper sulfide minerals are slowly oxidized by the air and that dilute sulfuric acid and iron (111) increased their solubility. At that time it was not known that bacteria were involved in the oxidation of the sulfide minerals. It has been shown that pyrite, molybdenite, free sulfur, and the copper sulfide minerals found in the waste rock dumps in Bingham Canyon, Utah, are largely oxidized by chemosynthetic autotrophic microorganisms found in the leaching streams.2-6 Similar organisms have been isolated in other mining areas7,8 and from the effluents from coal rnines.9 The following are some of the questions that have arisen regarding the mechanisms of the reactions involved in the leaching process. How dependent is the leaching operation upon the biological reactions? How does the temperature effect the biological and non-biological reactions? How does the concentration of iron (II) and (111) effect the rate of oxidation of copper (II) sulfide? Does the iron act as a catalyst? Does activated carbon act as a catalyst on the oxidation of sulfide minerals? What effect does the hydrogen ion concentration (pH) have on the above reactions? The purpose of this paper is to report the results of laboratory studies on these problems. EXPERIMENTAL The apparatus used in this investigation was an air lift percolator described in our earlier work.' The percolator consisted essentially of an air lift which enabled the leaching solution and microorganisms to pass freely through a suspension of mineral (substrate) in Ottawa sand. The air lift served the additional purpose of maintaining an ample concentration of oxygen and carbon dioxide in the nutrient (leaching) solution. (See Fig. 1.) The percolators were so constructed that they could be immersed in liquid constant temperature baths for temperature studies. The thermostats were controlled to +0.5°C. The reactions were all run in the dark. The percolators were charged with one to three g of mineral, dispersed in 100 g of Ottawa sand and 100 ml of nutrient or leaching solution. The sand was purified to remove traces of iron by digesting with concentrated hydrochloric acid and washng with distilled water until free from chloride. After drying, the sand was ready for use. The compressed air supply was regulated to 5 psi and bubbled through an aerator containing distilled water, which was maintained at the same temperature as the bath used. The air was filtered through cotton plugs to maintain sterile conditions. The tops of the

Jan 1, 1968

By R. W. Gould, B. G. LeFevre, A. G. Guy

The resistivity anomaly known as the K state was studied in Ni-Mo alloys containing 10.5 and 14.0 at. pct Mo. Both these alloys exhibit a large K effect which depends on the mechanical and thermal treatment. On the basis of X-ray diffuse scattering studies which were correlated with resistivity measurements, it appears that the K state in dilute Ni-Mo alloys can be associated with changes in the degree of short-range order within the a phase. An interesting phenomenon that has received much attention in recent years is the K state. The K state is marked by anomalous changes in some of the physical properties of certain alloys without the occurrence of observable microscopic structural changes. One of the early pieces of work in this area was by Thomas' who studied alloys of Ni-Cr, Ni-Cu, Ni-Cu-Zn, Fe-A1, Fe-Si, and Ni-A1. Upon annealing specimens which had been previously cold-worked or quenched from an elevated temperature he found an anomalous increase in resistivity over a certain temperature range. He also found that specimens which had been appropriately annealed to develop the K state showed a decrease in resistivity upon subsequent cold working. These effects are opposite to those found in normal alloys. Although the resistivity anomaly has been rather arbitrarily taken as the "definition" of the K state, there are several other interesting effects which accompany the resistivity increase. In Ni-Cr alloys,2, 3 for example, it was found that the hardness increases with increasing resistivity. It was also found that specimens which have been treated to develop the K state can be cold-worked for as much as an 80 pct reduction of area without an increase in the hardness. In Fe-A1 and Fe-Si alloys4 the K state is accompanied by an increase in flow stress and by a lattice contraction. In Ni-A1 alloys,5 specimens which have been treated to develop the K state also show an increase in elastic modulus. In Ag-Pd alloys6 the increased resistivity observed on annealing a cold-worked specimen is accompanied by an increase in the thermoelectric power and an increase in the Hall coefficient. The explanations of the K state phenomena are varied and depend upon the particular alloy in question. Several theories have been advanced to explain the increased conductivity with cold work on the basis of changes in the electronic configuration of the alloy as a result of local lattice distortions.7"9 Most investigators, however, believe that some type of local order in the solid solution, either short-range order (SRO) or clustering, is responsible for this effect. Theories concerning the relationship between ordering and the K state have for the most part been speculative, since there is little direct X-ray evidence that can be correlated with the above property changes. Much of the previous work on the K state was done in the Ni-Cr system where the small difference in the X-ray atomic scattering factors of the components nickel and chromium makes it very difficult to use X-ray diffuse-scattering measurements to determine the role of local order. In the Ni-A1 system, however, Starke et al.10 succeeded in detecting a connection between local order and the K state. It was found that a small but measurable K effect correlated with increasing SRO in the nickel-rich a phase. The manner in which local order might increase the resistivity of K state alloys is not completely clear. Since most of the known K state alloys contain at least one transition element, significance has frequently been attached to the presence of an unfilled d shell. It has been suggested that during the formation of the K state the number of conduction electrons decreases as a result of the transfer of s electrons to the d shell where they are more tightly bound.1'11'12 Koster and Rocholl13 have proposed that SRO can cause an increase in resistivity for alloy systems in which the number and mobility of charge carriers are reduced when the percent solute is increased. According to this hypothesis, the local environment of a given solvent atom changes in the same manner with increasing percent solute as it does with an increasing degree of SRO; hence the change in physical properties should tend in the same direction. In this hypothesis, SRO is considered only in a statistical sense, and the increased resistivity of the K state is attributed to a change in the mean distribution of electrons and holes in the s and d states as a result of SRO. From the work of Chen and Nicholson on Ag-Pd alloys,6 it appears that the K state can occur in systems for which the d shell is completely filled. These investigators explained the increased resistivity by picturing the SRO as small domains of some form of long-range order (LRO). According to ~ibson,'~ the number of effective electrons can be reduced by the creation of a new Brillouin zone boundary near the Fermi surface of an alloy as a result of the changing crystallographic symmetry that accompanies the formation of a superlattice. This idea may be expressed in terms of the superzone concept.15 In the present work the role of local order in the formation of the K state in Ni-Mo alloys was investigated. The principal tools used in this study were X-ray diffuse scattering and electrical resistivity measurements; however, these data were supplemented by electron microscopic and field-ion microscopic data. The purpose of the work was to determine whether or not the K state in Ni-Mo alloys can indeed be attributed to the formation of SRO as has been proposed by previous investigators.

Jan 1, 1969

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By A. V. Deforest, C. W. Macgregor, A. R. Anderson

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942