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By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.' He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich's equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger's study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970

By F. Weinberg

Measurements have been made of solute segregation during dendrilic growth by using radioactive solute elements and ,measuring the activity of den(12-ites cut from decanted specimens. This has been done for both lead awl tin based binary alloys contaitzing the following solute additions: Ag, T1204, was dependet on ko, the equilibrium distribution coefficient in the following way Fay k &apos;c 0.1, C/C 0.6; for k0 >0.1. 0.6 <c,/c,< I. Qualitative obse?-vations were madc of dendritic segregation, by using autoradiographic techniques, for the Sn + Ag110 and Sn + Tlo4 systems. The observation were found to he in general agreement with the measurements ofCA/Co. Autoradiographic were also obtained of scctiolccl delzr11-iie stalks. These indicated that the stalks had a substructure, dclileated by solute corzetlt?atio?zs nlolg the substructure walls. A new dendrite growth direction <JI2> is reported for tila. SOLUTE segregation in dilute binary alloys has been investigated by Pfann,&apos; Smith, Tiller, and Rut-ter,&apos; and others. They considered the case of a slowly advancing plane solid interface, and derived expressions for the distribution of solute in both solid and liquid during solidification. To determine these expressions, they assumed no diffusion in the solid and either complete mixing in the liquid:&apos; or diffusion controlled solute movements in the liquid without any convective mixing.&apos; The present investigation considers solute segregation during dendritic growth, in which case the solid-liquid interface is not plane, and the growth rates are rapid. Segregation under these growth conditions has not been treated mathematically, because of the relative complexity of the system. It has been suggested by Chalmer, on the basis of preliminary results, that an alternative to the diffusion and heat flow controlled conditions during growth is &apos;diffusionless" dendritic growth in which solid is formed with the same composition as the liquid. He suggests this type of growth may depend upon a solvent-solute relationship that permits some solid solubility without excessive increase in internal energy, as is the case for solutions of tin in lead. On the other hand, Montariol,4 and others, have shown experimentally that some segregation does occur during dendritic growth in metals using etching and radioactive tracer techniques to indicate the concentrations of the solute. The present investigation was undertaken to determine, both qualitatively and quantitatively, the extent of solute segregation associated with dendritic growth in a series of binary alloys, as a function of solute concentration. PROCEDURE The solvent materials used were Vulcan Electrolytic tin (99.997 pct purity) and Tadanac lead (99.998 pct purity). The solute materials were Zn, Sn, and Sb (better than 99.998 pct purity), Ag and Co (99.5 pct purity), and T1 (Fisher "purified" metal sticks). Activation of the solute metals was carried out in the reactor at Chalk River, Canada. Master alloys were prepared by induction heating from the radioactive solute metal and the pure solvent, under argon, in graphite crucibles. Pieces of these alloys were then added to the solvent to give the required solute concentration. Dendrites were grown in essentially the same manner as that described by Weinberg and Chalmer, , in which controlled orientation single crystals were grown dendritically in horizontal graphite boats, and the liquid decanted. The crystals were grown and decanted in an atmosphere of tank argon. Before decanting, a sample of the liquid was drawn up in a glass tube and allowed to solidify rapidly. The orientations of the single crystals were such that <loo> was parallel to the growth direction, and (100) in the horizontal plane for lead, and [1101 and (110) respectively for tin. With these orientations long dendrite stalks formed along the bottom of the boat in the dendrite direction (<100> for lead and [I101 for tin) from which secondary branches grew. Only these secondary branches, which grew freely in the liquid from the dendrite stalk to the liquid surface, were used in the measurements. Accordingly, effects due to substrates and oxides on the surface of the liquid need not be considered. In order to measure the solute concentration C, of the dendrites, individual dendrite stalks were cut from the decanted specimens, remelted, and formed

Jan 1, 1962

By A. J. Williams

THE province of Saskatchewan, situated in the center of the Great Plains region of Canada, has, like most prairie areas, an essentially agricultural economy. Most of its population of about 860,000 is located in the southern half of the province in the farming and ranching areas. To the north of the prairie is a broad forested belt supporting a considerable timbering industry, and the northern one third of the province is glaciated pre-Cambrian rock formation. This latter area is relatively barren of vegetation, but the presence within it of a considerable variety of radioactive, noble and base metals, and industrial minerals has been shown by prospecting in recent years.&apos; Glacial Geology The Keewatin ice sheet, considered to have accumulated in the country to the west of Hudson Bay in Pleistocene time, covered at its maximum advancement almost all of Saskatchewan and extended south of the international boundary. Only in the Cypress Hills in the southwest and around Wood Mountain in the south central portion of the province did the preglacial formations escape the action for this glacial period. The bedrock of the plains and forest areas therefore is overlain by moraines and modified glacial drift, which vary in thickness from a few feet to 400 or 500 ft.&apos; Glacial action in the pre-Cambrian area of the province was largely erosional, most of the more recent formations and some of the pre-Cambrian rock being transported out of the area to the south and west. It has been estimated that about 13 pct of this area is composed of lakes and rivers not too adaptable to rail or water transportation, so that until the use of aviation for exploration purposes became general, development of the area was slow. To the south, the heavy mantle of glacial drift has to some extent deterred the discovery of industrial minerals in the bedrock underlying the forest and prairie regions3 At the same time, this drift contains numerous deposits of those most elementary and necessary industrial minerals, sand and gravel. Sedimentary Basin The major feature of the sedimentary deposits underlying the plains regions is the basinal structure known as the Moose Jaw syncline, which runs from the southeast corner of the province in a northwesterly direction. To the west of this syncline the formations curve upward, then have been faulted and further upthrust to appear at the surface in the foothills of the Rockies in Alberta; to the east and north they curve upward into Manitoba and northern Saskatchewan, but the surface contacts are covered mostly with glacial drift.238 The axis of the syncline dips to the southeast, so that there is also an upward trend of the formations along the axis to the northwest. In illustration of the regional structure underlying the province, the pre-Cambrian basement has been logged in drillholes at the following depths in several locations: Ogema (south central), 9390 ft; Gronlid (northeast), 2599 ft; Vera (northwest), 4422 ft; Big River (north northwest), 2348 ft. Fig. 1 indicates the general surface geology of the province, ignoring such glacial overburden as may overlie many of the bedrock formations. Also indicated is the approximate location of the axis of the Moose Jaw syncline.&apos; Industrial Minerals Clays: The province is fortunate in possessing a widespread distribution of clays of ceramic value, ranging from those used for heavy structural products to the high grade pottery and china clays. Shales suitable for brick and tile production are found in the Upper Cretaceous and Tertiary formations across the south of the province where the glacial drift is thin or nonexistent. Many deposits of glacial lake clays suitable for such wares are found scattered over the rest of the province south of the pre-Cambrian area. The Whitemud formation of the Upper Cretaceous is a narrow sedimentary band of secondary clays found intermittently at points across the south of the province where glacial action did not disturb or remove them.&apos; In the southwest corner of the province, around Eastend in the Frenchman River valley, the refractory clays of this formation are contaminated somewhat with iron compounds or other alteration products of basaltic rocks. This eliminates the use of those clays in true whitewares, as they fire to creamy buff shades at the lower temperatures and to a blue-specked grey at cone 8 to 12, (2280°F to 2390°F), the range commonly used in firing whiteware. However, for use in the production of colored artware, caneware, stoneware or crockery, and sewerpipe, this type of clay makes an excellent body that requires little or no addition of flint, feldspar, or other fluxing materials such as are required in the higher class of ware.&apos; It is not a grade of clay that can be shipped great distances to the manufacturing centers, but a market for considerable tonnages has developed at nearby Medicine Hat, where cheap natural gas is available for the firing of the ware. Farther east in the south central portion of the province, the clays of the Whitemud formation are generally more refractory and white burning. The formation is divided into three zones, consisting of white clays, brown shale, and white sandy clays.

Jan 1, 1953

By Carl Benedicks

IT is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).1 A study of the microstructure or local chemical composition of the metal (iron; 70 :30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point-to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the fact that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion"2 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."&apos; In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corrosion."4 On consulting the many textbooks on corrosion, as that

Jan 4, 1925

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

IN the footnote on the first page of Prof. Stoek&apos;s paper, as printed in vol. xxviii. of the Transactions, I alluded to him, under an erroneous impression, for which he was in no way responsible, as " the present Director of the Scranton Schools." This incorrect statement placed him in a false position, as possibly having authorized the use of a title to which he had no claim. In fact, Prof. Stoek has never had any official connec-

Jan 1, 1900

By E. Hornbogen

Discontinuous precipitation in a iron can occur by at least two different mechanisms. These mechanisms are compared, using observations made on an Fe-22 at. pct Zn alloy and an Fe-19.5 at. pct Mo alloy. In the Fe-Zn alloy, precipitation began on grain boundaries. These boundaries moved into the supersaturated solid solution, providing nucleation sites and an easy path for diffusion. The precipitated phase pew as lamellae, perpendicular to the PRECIPITATION reactions are called discontinuous if the nucleation of particles does not occur on individual sites in the supersaturated matrix.&apos; In discontinuous precipitation, nucleation and growth occur on a reaction front that moves into the supersaturated solution and leaves a two-phase aggregate behind. The term cellular precipitation2 has also been used, but the term autocatalytic precipi- moving reaction front. The orientation of the depleted iron differed from that of the supersaturated iron. In the Fe-Mo alloy the growing precipitate particles apparently created dislocations in the growth front which served as nucleation sites. The precipitate grew on (110) planes of the iron, and growth occurred through volume diffision. The depleted iron retained the orientation of the supersaturated solid solution. tation seems to describe the nature of such reactions best. The basic effect of such a precipitation mechanism in a solid is that it is able to move or create sites that can catalyze nucleation. Such sites can be grain boundaries and dislocations. A mechanism of autocatalytic precipitation must, therefore, include some rational process by which a grain boundary may move into the supersaturated matrix or by which dislocations may be generated in front of the reaction. Discontinuous precipitation is always in competition with individual nucleation and growth of par-

Jan 1, 1963

By Douglas Bunting

In the anthracite fields of Pennsylvania, mine fires occur with more or less regularity and their existence is an ever-present hazard in coal mining. In all probability 90 per cent. of the mine fires can be ascribed directly or indirectly to the ordinary miner&apos;s open lamp. Other causes may be smoking, electrical installations, gas explosions, gas feeders, and the communication of fire to the outcrops from ash dumps, culm banks, timber and brush fires. Fires in pump rooms, engine rooms, and barns have been largely eliminated as a result of the Act of Assembly, approved June 15, 1911, which provides that all inside buildings, including engine rooms, pump rooms, barns, etc., shall be constructed of incombustible materials. Smoking of pipes, cigars, and cigarettes should be prohibited in the mines and too much care cannot be exercised in preventing fires by enforcing all rules designed for that purpose. Mine fires that involve underground fighting are invariably dangerous, and all fires, irrespective of the method pursued in extinguishing them, involve property loss and expense. Each fire generally presents a more or less original problem, dependent on the particular conditions. Generally mine fires may be divided into two classes: Those occurring in inaccessible workings and those occurring in accessible workings. The methods pursued in extinguishing or controlling mine fires are as follows: (I) direct attack, (2) smothering by sealing, (3) flushing with silt or other solids, (4) flooding with water, (5) cutting off, (6) surrounding with incombustible materials, (7) digging out by stripping from the surface. Most fires arc extinguished in their incipiency by direct attack and failure to extinguish by this method is due to late discovery, lack of water, and facilities for fighting, or improper procedure in the initial attack. Should the method first pursued be unsuccessful, careful consideration should be given in determining next the method to be adopted; then the work should be carried on as rapidly as possible and under the supervision of the most competent persons. Materials and supplies should be furnished without delay and in sufficient quantities for the work to be accomplished.

Jan 1, 1922

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of &apos;impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By R. B. Burt, James A. Barr, I. S. Tillotson

THE pumping of solids in water suspension is an important part of many metallurgical and mining operations. In most cases, it is still in the rule of thumb category for which no universal formula has been developed, and much research is needed. Because of the limited and incomplete data available, this article may be classed as an experience paper, which is presented with the hope that some contribution will be made toward the development of the so-called universal formula. This formula, if and when developed, may be evolved from several factors, many of which are not now available for general application. The designing engineer is interested in obtaining accurate forecasts on: 1-the minimum velocities needed to prevent choke-ups in the pipeline, which in turn dictates pipe sizes, 2-power required for pumping, 3-pump selection. The basic factors for a given problem will include: 1-weight per unit of time of solids to be handled, 2-specific gravity of solids, for calculation of volume, friction and power, 3-screen analysis of solids with the colloidal acting, i.e., the slime fraction, a very important factor, 4-shape of particle or some means of determining a friction constant, 5-effects of percentage of solids, 6-development of a viscosity factor to be used in the overall calculations, 7-calculation of the lower limits of pipeline velocities permissible, 8-calculation of total head, pump horsepower, and 9-setting up of pump specifications. In certain limited cases horsepower and total heads and minimum velocities may be computed and a suitable pump selected from basic data, but in many cases, as in mining of Florida pebble, phosphate, experience rather than a hydraulic formula still should be used as a basis of selection. Pumping Florida Pebble Matrix Pumping at the Noralyn mine of International Minerals and Chemical Corp. will be used as an example. Other areas will vary as to the characteristics of the matrix, especially the slime content. A typical screen analysis of this matrix is: +14 mesh, pebble size,* 2.1 pct; -14 +35 mesh, 11.4 pct; -35 +150 mesh, 60.5 pct; -150 mesh, 25.0; total, 100 pct; moisture in bank, 20.0 pct; weight per cu ft in bank, 120 lb. The -150 mesh fraction may increase to as much as 35 pct in adjacent areas. When thoroughly elutriated, the matrix has a relatively slow settling rate, which is an important factor in permitting lower pipeline velocities without choke-ups. Exact data is not available to evaluate settling rates. For a factor of 100 a suspension of clean building sand in water is suggested. When pumping long distances, a quick settling matrix allows the coarser solids to settle out along the bottom of the pipeline, causing drag, turbulence, and increased friction. With a slow settling matrix as at Noralyn, turbulence acts to keep the solids in suspension at a lower friction head, regardless of the pumping distance. When the pebble, content of the matrix, i.e., the +14 mesh fraction, is in excess of 10 pct of the total solids, trouble may be expected from settling out even in normal pumping distances. To prevent choke-ups and maintain tonnage, an additional pump must be added in the long runs, where one pump would otherwise be satisfactory. A typical pulp handled is: total volume, 7800 gpm; water, 4500; solids pumped per hr, 4200 lb; sp gr pulp, 1.4; percent solids in pulp, 46.; pipe size, 16-in. ID; pulp velocity, 12.85 fps; probable critical velocity, 10 fps, as below this minimum -velocity choke-ups would be numerous. In calculating friction heads the Armco handbook is used where a roughness factor based on 15-year-old pipe is set up. Because the pipe used in pumping matrix is, smooth and- polished because of the scouring, action of the phosphate and its silica content, the head losses in the Armco table for water are practically the same as in pumping the Noralyn matrix through smooth pipe, plus the fact that conditions vary widely over short periods, making accurate determinations difficult to obtain. New pumps and pump, changes are being tested continuously and a wealth of data built up. This has resulted in a substantial improvement and lower relative costs in pumping matrix. The Florida phosphate industry is constantly seeking to offset higher wage and material costs with improved technique. Until a few years ago a 12-in. discharge pump was commonly used, with heads as low as 80 ft. Sizes have gradually increased and heads more than doubled. For example, the following pump was placed under test at the Noralyn mine: make, Georgia Iron Works; size, suction 16 in., discharge 14 in.; impeller, 39-in. diam; motor, 600 hp, slip ring; full load speed, 514 rpm. The results were increased head, higher capacity than the older design, with fewer pumps in the line from mine to washer.

Jan 1, 1952

ENGINEERS AVAILABLE (Under this heading will be published notes sent to the Secretary of the Institute by members or other persons.) Recent graduate desires position as surveyor or assistant to mining geologist. No. 112. Member, technical graduate with varied experience covering milling, cyaniding, plant design, mill and dam construction, underground work, and executive, examination and reporting on mining properties, desires position as superintendent of gold and silver property in United States or Latin America. No. 113.

Jan 7, 1914

By Henry M. Howe

Preparing the Metals.—Ordinary silver wire was hard-drawn to No. 23 Brown and Sharp gauge; it was cut in two, and one piece was carefully annealed in the ordinary way. The wire was prepared by Messrs. Guild and Delano, jewelers, Boston. The Ansonia Brass and Copper Co., Ansonia, Conn., kindly furnished me with some hard-drawn copper wire No. 31, A. W. G., and some of the same wire after annealing in the ordinary way.

Jan 1, 1885

By Fred P. Dewey

The product of the Muirkirk, Md., furnace has always enjoyed a very high reputation for strength ; and this is supported not only by its behavior in practice, both alone and in mixtures, but also by the following series of tensile tests, made at various times during the last fourteen years: South Boston Iron Co., November loth, 1874. Strength. Pounds Grade. per square inch. Density. No. 3,....... 30,685 7.2794 No. 4,....... 35,140 7.2713

Jan 1, 1889

By W. N. Poundstone, P. C. Thakur

Introduction Horizontal drilling in coal mines is a relatively new technology. The earliest recorded drilling in the United States was done in 1958 at the Humphrey mine of Consolidation Coal Co. for degasification of coal seams. Spindler and Poundstone experimented with vertical and horizontal holes for several years. They concluded in 1960 that horizontal drilling in advance of underground mining appeared to offer the most promising prospect (for degasification) but effective and extensive application would be dependent upon the ability to drill long holes, possibly 300 to 600 m, with reasonably precise directional control and within practical cost limits (Spindler and Poundstone, 1960). Mining Research Division of Conoco Inc., the parent company of Consolidation Coal Co., began a research program in the early 1970s to achieve the above objective. The technology needed to drill nearly 300 m in advance of working faces was developed by 1975 and experiments on advance degasification with such deep holes began in 1976. Preliminary results of this research have already been published (Thakur and Davis, 1977). To date nearly 4.5 km of horizontal holes have been drilled for advance degasification and earlier results were reconfirmed. In summary, these are: • The greatest impact of these boreholes was felt in the face area where methane concentrations were reduced to nearly 0.3% in course of two to three months from original values of nearly 0.95%. • The methane concentration in the section return reduced to 50% of its original value immediately after the boreholes were completed, indicating a capture ratio of 50%. • The total methane emission in the section (rib and face emission plus the borehole production) did not increase but rather gradually declined with time. • Initial production from 300 m deep boreholes in the Pittsburgh seam varied from 3 m3/min to 6 m3/min but then slowly declined as workings advanced inby of the drill site (well head) exposing a larger surface area parallel to the borehole. Encouraged by these results, it was decided to design a horizontal drilling system that would be mobile and compatible with other face equipment. A mobile horizontal drill can be divided into three subsystems: the drill rig, the drill bit guidance system, and borehole surveying instruments. The drill rig provides the thrust and torque necessary to drill 75- to 100-mm diam holes up to 600 m deep and contains the mud circulation and gas cuttings separation systems. The drill bit guidance system guides the bit up, down, left, or right as desired. Borehole surveying instruments measure the pitch, roll, and azimuth of the borehole assembly. Additionally, it also indicates the thickness of coal between the borehole and the roof or floor of the coal seam. Thus, it becomes a powerful tool for locating the presence of faults, clay veins, sand channels, and the thickness of coal seam in advance of mining. In recent years, many other potential uses of horizontal boreholes have come to light, such as in situ gasification, longwall blasting, improved auger mining, and oil and gas production from shallow deposits. The purpose of this paper is to describe the hardware and procedure for drilling deep horizontal holes. The Drilling Rig [Figures 1 and 2] show the two components of the mobile drilling rig: the drill unit and the auxiliary unit. The equipment (except for the chassis) was designed by Conoco Inc. and fabricated by J. H. Fletcher and Co. of Huntington, WV. The drill unit. It is mounted on a four-wheel drive chassis driven by two Staffa hydraulic motors with chains. The tires are 369 X 457 mm in size and provide a ground clearance of 305 mm. The prime mover is a 30-kw explosion-proof electric motor which is used only for tramming. Once the unit is Crammed to the drill site, electric power is disconnected and hydraulic power from the auxiliary unit is turned on. Four floor jacks are used to level the machine and raise the drill head to the desired level. Two 5-t telescopic hydraulic props, one on each side, anchor the drill unit to the roof. The drill unit houses the feed carriage, the drilling console, 300 m of 3-m-long NQ, drill rods, and the electric cable reel for instruments. The feed carriage is mounted more or less centrally, has a feed of 3.3 m, and can swing laterally by ± 17°. It can also sump forward by 1.2 m. The drill head has a "through" chuck such that drill pipes can be fed from the side or back end. General specifications of the feed carriage are: [ ] The auxiliary unit. The chassis for the auxiliary unit is identical to the drill unit but the prime movers are two 30-kW explosion proof electric motors. It is equipped with a methane detector- activated switch so that power will be cut off at a preset methane concentration in the air. No anchoring props are needed for this unit. The auxiliary unit houses the hydraulic power pack, the water (mud) circulating pump, control boxes for electric motors, a trailing cable spool, and a steel tank which serves for water storage and closed-loop separation of drill cuttings and gas.

Jan 1, 1981

By A. B. Parsons

NOT every organization on reaching the relatively ripe age of three score and fifteen can say with truth that its purpose and objects remain precisely the same as prescribed by its founding fathers. Of course, constancy of purpose may be something else than unalloyed virtue. It could merely reflect slavish worship of tradition, intellectual stagnation, or sheer inertia. On the other hand, it could establish the fact that the founders were men possessed of broad outlook, of prophetic vision, and of an acute sense of direction. In addition to charting the course with precision, the founders of the A.I.M.E. surely showed a flair for expressing clearly in a few words what others might say obscurely in many words. To quote verbatim from the "call" for the meeting, in 1871, the proposed organization was to have: "two great objectives: "First, the more economical production of the useful minerals and metals. "Second, the greater safety and welfare of those employed in these industries." This text underwent some refining on several subsequent occasions but today the ultimate product, as set forth in the Constitution reads: "to promote the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by all lawful means." The original call was dated "Wilkes-Barre, Pa., April, 1871," and was signed by Eckley B. Coxe, of Jeddo, and by R. P. Rothwell and Martin Coryell, both of Wilkes-Barre, each of the three subscribing himself as "mining engineer." The authors proceeded to explain briefly just how it was proposed to achieve these objectives: "In European countries, where the arts of mining and metallurgy have long been the subject of the most careful study, no means have been found so effectual in attaining the end above proposed, as the free interchange of experience among those actually engaged in these industries; and this object has been accomplished mainly through the medium of `Institutes,&apos; `Associations,&apos; or `Societies,&apos; composed of those engaged in these occupations, and by the periodical publication of `essays&apos; or `papers&apos; communicated to such societies by their members. "It must be evident to all practical men that the interchange of the varied experience

Jan 1, 1947

By A. E. Nehrenberg

THE mechanism by which austenite forms in steels has received a great deal of attention in the literature in past years.&apos;-&apos;* Our present knowledge concerning this mechanism has been recently summarized quite concisely by Bain and Vilella,1 while a few years ago the literature was carefully reviewed by Roberts and Mehl.² The consensus is that any ferrite-carbide interface is a potential site for the nucleation of austenite during heating above the Acl temperature, and that the new austenite generally grows freely to produce approximately equiaxed grains, whether the carbides are initially present in the lamellar or the spheroidal form. In the case of eutectoid steels, growth of the new grains of austenite continues until contact is established with other grains. Then growth stops and an initial austenite grain size is established which does not change until the heating is continued to some high temperature at which grain coarsening begins. In the case of pearlitic steels which are not of eutectoid composition, the proeutectoid ferrite or carbide may interfere with the growth of the austenite if the temperature is not above that designated the A63 or the Acm, respectively. Although a large amount of work has been done to establish the mechanism of austenite formation in steels, it became clear to the present author while he was studying the transformation characteristics of a new 0.25 C Mn-Si-Ni-Mo hypoeutectoid steel" that the manner in which austenite grows in steels depends upon some factor, or factors, not previously considered. This was indicated by the fact that when this steel in the spheroidized condition was heated above the Ae1 temperature the new austenite which was formed did not envelop the carbides and grow in an equiaxed manner as described by Bain³ or spheroidized steels. Instead, in this steel, the austenite was observed to grow much more readily in certain directions than in others with the result that at temperatures within the Ac1-Ac³ ransformation range the austenite grains were acicular in shape. The excess ferrite was also found to be acicular with the distribution of these phases being such that a lamellar pattern was developed. This unusual directional growth of austenite in this new steel initially in the spheroidized condition is illustrated by fig. 1. A search of the literature revealed that this type of growth was not necessarily peculiar to this steel for similar microstructures had been observed by other investigators.4-8 However, the full significance of these microstructures does not appear to have been appreciated, and no work has been done to determine the conditions responsible for this directional growth of austenite or to arrive at an understanding of it. It was for this purpose that the work described in the present paper was carried out. Material: During the course of this investigation a total of 15 steels was studied. They consisted of hypoeutectoid, eutectoid and hypereutectoid carbon steels, and hypoeutectoid and hypereutectoid alloy steels, all of which were obtained in the annealed condition from commercial warehouse stock. As received, the carbon and alloy hypereutectoid steels had microstructures which consisted of spheroidal carbides in ferrite, whereas the eutectoid steel and the hypoeutectoid steels were pearlitic. The grades of steel represented were 1050, 1080, 10110, 3310, 4140, 4340, 4615, 6145, 8620, 9260, 9442,

Jan 1, 1951

By Wilbur H. Grant

THE property of the United Comstock Mines Co. lies in the eastern foot-hills of the Sierra Nevada Mountains, in the Washoe mining district of Storey County, Nev. Commencing at the boundary line between Virginia City and Gold Hill, covering all the town of Gold Hill, it extends south to American Flat; the main camp, or the new town of Comstock, the mills, shops, residences of employees, and the main haulage-tunnel portal are located on American Flat. The property extends for about 10,300 ft. along the lode; this covers the southern end of the main Comstock lode, the Knickerbocker branch, and the junction of the Silver City branch with the Comstock lode. Within the property, 5000 ft. of the main Comstock lode is known to have been productive, 1000 ft. of the lode at the northern end of the property is thoroughly developed, and 1000 ft. south of this is partly developed; this leaves about 3000 ft. of the known productive portion that has not been opened up by this company. The northern end of the property, or the Imperial mine, has been intricately developed by five main levels and numerous sublevels. The Yellow Jacket ground to the south has been partly developed by the reopening of three old levels. In addition, the main haulage level is driven from the portal at Comstock for 9250 ft., to the north end of the property; about 5500 ft. of this `is in the foot wall of the lode and parallel to it.

Jan 11, 1922

By L. G. Austin, R. R. Klimpel

This article demonstrates that the Gilvarry and Klimpel-Austin equations for the random fracture of solids are incorrect by deriving intuitively correct expressions for simple cases and showing that the foregoing equations do not reduce to right answers. It is the purpose of this article to point out serious errors in some existing treatments of the random fracture of solids. Gilvarry &apos; gives the equation where B(y,x) is the cumulative fraction by weight of particles which fall below size y when particles of size x are broken. The constants i, j, k contain shape factors and densities of flaws leading to propagating fracture surfaces. The authors believe this equation to be incorrect. Klimpel and usttin&apos; give where r~ is the number of fracture planes originating from edge flaws (per L where L is the edge length of the original particle), rs is the number of fracture planes originating from flaws on the particle surface (per S where S is the surface of the original particle) and rv is the number of fracture planes originating from flaws within the particle volume. This equation is also incorrect. The failures of these equations will be demonstrated by deriving intuitively correct expressions for simple cases and showing that the Eqs. 1 and 2 do not reduce to the correct answer. In this process, the flaws in statistical reasoning inherent in the derivations of Eqs. 1 and 2 become apparent. THE KLIMPEL-AUSTIN EQUATION Eq. 2 was derived by considering a set number of fracture planes occurring spatially at random within a given particle. This case will be treated here in its simplest form: a line with 1, 2, 3, etc., fractures occurring at random. This is illustrated in Fig. 1, with the original length of the line as Vo. The breakage of a long, thin, brittle fiber is a corresponding physical case, with the volume of a fragment proportional to its length. Assuming independence of the occurrence of the fractures, the probability of any one fracture occurring in length dV is dV/V0. The probability of the first fracture occurring at a length V to V + dV is dV/Vo. For the case of only one fracture per particle, formation of a number-size distribution of the left-

Jan 1, 1969