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By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett', Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,'. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By Frank L. Gaddy

Falls of roof account for over 50% of the fatalities that occur in coal mines in the US. Thus, roof control is one of the more important phases of underground mining. In reality, the control of roof influences the system of mining and is a major determinant of the width and spacing of working places, operations at the mining face, ventilation control, and surface subsidence. Frequently, the control of roof is the largest single cost item. Roof control is a never-ending task, not only at the working face and throughout sections where men are working, but along haulways and air- ways that must be maintained for the life of the mine. This is because roof, even the best of roof, slowly deteriorates, so it must be frequently examined, with corrective support applied when needed. As coal is excavated, stresses are set up in the roof because the previous equilibrium is upset, resulting in pressures that cause fractures and slight movements that are frequently hard to detect. Unless the immediate roof, in the excavated area, is given support by artificial means, it might fall or there might be a succession of falls, varying from a thin scale to several feet, depending on the nature of the top. Exceptions to this are those rare mines, or sections of mines, with hard, strong, nonweathering roof that requires no support. GENERAL CLASSIFICATION OF ROOF There are two broad types of roof as far as support is concerned: the immediate roof above the coal and the main roof. Artificial support for mining purposes is only concerned with the immediate roof as nothing except large blocks of solid coal, or massive concrete, will support the main roof. The immediate roof is generally a few feet thick but can vary from inches to 6.1 m (20 ft) or more. There are examples of where there is no immediate roof as the massive main roof lies directly on the coal

Jan 1, 1981

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization'" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.' Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954

By Albert R. Ledoux

I AM indebted to The Kaolin Co. of West Cornwall, Conn., and particularly to its engineer, Mr. M. Wanner, for permission to make public, through the Transactions of the American Institute of Mining Engineers, the interesting results of his experiments, having in view the winning of kaolin from deep deposits without shaft-sinking or removing of the overburden. So far as I am aware, nothing like it has been accomplished heretofore, although it reminds one of the methods successfully employed in Louisiana for the winning of sulphur from deep beds by the sinking of pipes one within another, injecting superheated steam under pressure through one pipe, the heat of the steam liquefying the sulphur and the pressure forcing it up through the other pipe to bins at the surface. The kaolin-deposit at Nest Cornwall is an alteration in situ-that is, it is not sedimentary. A series of clay-veins dipping about 500 from the vertical, lie between a foot-wall of limonite and a hanging-wall of gneiss and hornblende schist. The clay-veins alternate with veins or seams of more or less broken quartz, and unaltered feldspar. The deposit, which occurs at a point about 600 ft. above the Housatonic river, was opened five years ago, and about 5,000 tons of a superior grade of washed kaolin has been extracted from open pits and sold. It soon became evident that this node of extracting the product would prove unremunerative, by reason of the dip of the vein and the intercalary strata and lenses of -quartz, and a more satisfactory method of working the deposit was sought. It is well understood, that, in the preparation of all clays for market, especially residuary kaolin, the most important as well as the most difficult step is the washing of the crude product. The difficulties increase with the percentage of foreign matter, especially quartz and mica, contained in the product, hence a sys-

May 1, 1906

By Max Y. Seaton

THE scope of this paper will be limited to finished materials that contain a large preponderance (around 80 per cent or more) of magnesium oxide. The large and commercially important production of refractory dolomite and modified dolomites is not discussed here, and the production of magnesium basic carbonate for use as a heat insulator is barely mentioned. The discussion is confined mainly to magnesias produced in comparatively great quantity by direct processing of naturally occurring raw materials and hence excludes secondary or highly purified products such as pharmaceutical products or U.S.P. light and heavy calcined magnesias of commerce. NOMENCLATURE The nomenclature of the magnesia products that will be discussed is somewhat confusing, in that it is customary in the trade to designate as "calcined magnesite" the materials that result from the calcining of magnesite to temperatures that remove the contained carbon dioxide. The finished product, therefore, is not magnesite at all but simply a more or less pure magnesium oxide or magnesia. Furthermore, partly for statistical and partly for commercial reasons, it has been customary, during recent years, to classify as "calcined magnesite" products that result from the heat-treatment of magnesium hydroxide precipitated from magnesium-containing brines; products that, obviously, have no relationship whatever to magnesite. In the listing of magnesia-containing materials, tonnages of which are regularly reported by the Bureau of Mines, reports ordinarily are made under two headings: "caustic calcined" magnesite, in which all of the varieties of products treated at relatively low temperatures are lumped; and "dead-burned" magnesite, in which are included both high-purity and low-purity, and particularly both high-iron and low-iron, materials that have been so heat-treated that the magnesium oxide occurs predominantly as crystalline periclase-materials used almost entirely for refractory purposes. In 1940 the apparent domestic consumption of "caustic calcined" magnesite was approximately 17,000 tons, about 95 per cent of which was produced in this country. The apparent consumption of "dead-burned" magnesite was approximately 172,000 tons, some 82 per cent of which was domestically produced. In both total quantity and percentage of material produced within the United States, these figures are record highs for many years past. UTILIZATION As indicated by these figures, the major tonnage outlet for magnesia is the refractories industry, in which magnesia is employed principally in three ways: (I) as dead-burned grain magnesite for the construction and maintenance of the hearths or bottoms of basic open-hearth furnaces; (2) in the form of refractory magnesite bricks and shapes; and (3) as a chemical

Jan 1, 1942

By AIME AIME

MINERALS and mineral resources are recognized as one of the things that nations are prone to quarrel about. The territory that was arbitrarily incorporated into the Polish Republic after the World War produces a variety of essential minerals on a substantial scale. The accompanying table has been compiled to give some idea of the relative importance of this production. Poland, before the recent war started, had an area of 150,000 sq.mi., just a little larger than the State of Montana. Its population was 32,000,000, equal to that of New York, New Jersey, Pennsylvania, Connecticut, and Massachusetts. Though not a highly industrialized country it nevertheless has important mines, steel plants, petroleum refineries, and sundry metal-fabricating manufactories. Coal, petroleum, iron and steel, zinc, lead, pyrite, potash, and salt are produced in excess of the country's domestic consumption. It has no appreciable production of copper, chromium, tungsten, nickel, tin, mercury, manganese, aluminum, magnesite, fluorspar, or graphite.

Jan 1, 1939

By C. A. Heberlein

The present war in Europe seems to have stimulated the demand for quicksilver. In July last, the price ranged around $35 per flask of 75 Ib., while to-day it seems to fluctuate between $47.50 and $50. The use of quicksilver in the form of fulminate, containing 70 per cent., and as corrosive sublimate, containing 73.8 per cent., must be extensive and a further market advance may be expected. With such an advance, some revival in quicksilver mining may be looked for, particularly in California, where many abandoned properties exist. What can be done with low-grade quicksilver ores under favorable conditions, particularly with low mining cost, may be seen from the following description of the Oceanic mine, near San Luis Obispo, Cal. Its operations date back to 1876, when rich sand ores were discovered. In three years 7,400 flasks of quicksilver were produced, but since then the deposit has been worked only sporadically . Until two years ago various attempts had been made by the Oceanic Quicksilver Co. to mine the more refractory "mud rock," which was encountered lying beyond the " sand rock." Mud and sand rock in varying quantities were treated together, with poor results, but operations were successful with sand rock of fair percentage. About two years ago, when all the sand rock had been exhausted, Murray Innes purchased the Oceanic mine. He found large quantities of low-grade mud rock, varying from 6 to 8 Ib. of quicksilver per ton, which at the prevailing low price of quicksilver demanded very cheap mining costs, in conjunction with high but cheap metallurgical extraction. At that time the extraction of quicksilver from mud rock ranged between 40 and 50 per cent., as far as I am able to learn. Mining The low cost of mining was the principal consideration, since, with mercury at 50c. per pound, the total gross value of the ore did not exceed

Jan 1, 1915

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,'-!' other investigators have encountered difficulty with the method."'. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By Paul D. Merica

One of the most useful, and at the same time least commonly used, methods of thermal analysis for the determination of transformations in metals and alloys consists in the recording of the time intervals required for successive increments of temperature change during heating or cooling, the temperature of the furnace containing the specimen being altered at a uniform rate. The curve obtained by plotting these time intervals as a function of the mean temperature of the specimen durnig the interval is called the inverse-rate curve. It is probably due to the fact that no simple and convenient method has apparently been available for the measurement of the successive time intervals that this method has not been so generally used as, for example, the differential method, for which several types of automatic or semi-automatic apparatus have been designed. Whenever this method has been used, the intervals have usually been measured with the use of a chronograph; its operation as practised at the Bureau of Standards1 is as follows: The temperature of the specimen is measured by a thermocouple and a dial potentiometer. The operator sets the potentiometer at successive values of the electromotive force differing by equal increments, usually 0.02 millivolt, and records the exact instant on the chronograph, by pressing a contact key, at which the galvanometer coil passes through its null position. Two-second intervals are also recorded on the chronograph record, and the number of seconds elapsing between successive signals is afterward counted from the record and plotted as a function of the electromotive force or of the temperature. This is an admirable method and by it most minute thermal arrests may be detected, but it requires a good chronograph, which is generally difficult to obtain, and the time of one operator during the recording and, subsequently, to read the intervals from the record; the latter operation often takes from one to two hours. There is here suggested a simple, convenient, and, it is believed, equally accurate method of recording the successive time intervals, by which the

Jan 1, 1921

By C. G. Black

THE purpose of this paper is to present data obtained from an investi-gation conducted on the grindability of coal by the American Society for Testing Materials Tentative Standard ball-mill method. This investiga-tion has been conducted over a period of a year, during which time several hundred tests were run on a wide selection of different coals coming from Pennsylvania, Ohio, West Virginia and Kentucky. The data herewith presented tend to show that the tentative standard ball-mill method might give results that are misleading and that a volume measure might be more indicative of the true grindability 'of materials of varying specific gravity. A means whereby the time element might be reduced has been studied and other phases of this work such as preparation of samples, mechanical screening, reporting results and duplicating tests have been investigated. It is hoped that all criticism offered in this paper will be taken as constructive, with the purpose in mind of perfecting the method now tentative to show the true conditions and of making optional the manner in which certain parts of the test might be conducted to meet diversified laboratory conditions.

Jan 1, 1936

By J. Parke Channing

IT IS most appropriate for mining engineers and in fact for all engineers to perfect themselves in leader-ship, because in the last ten years there has been a growing realization on the part of capital that there is no man who by capacity and training is better fitted to manage industrial production than the engineer. In high places the engineer and particularly the mining engineer is coming into his own. We have Mr. Hoover as Secretary of Commerce, Mr. Hammond as the head of the Federal Fact-finding Coal Commission, and Prince Caetani as Royal Italian Ambassador, all mining engineers. More and more in all industries is the manager more likely to be an engineer than he was five, ten, fifteen or twenty years ago, and the feeling is that the man who has had a technical training, whether from going to a school or from burning the midnight oil, makes a better manager than the man who has not. We find in mining that the best man for a manager is one who has had engineering, training. The manager who comes up from the office, from the purchasing department or from the transportation department may make a fairly good manager but he is never so good as the man who has had a technical training. He cannot speak the language of his staff.

Jan 5, 1923

By A. J. Erickson, W. W. Atkinson

Concepts developed in a geologic data recording system at the Victoria, Nevada breccia pipe-skarn copper mine, are not fundamentally new, but represents expansion of earlier ideas. The basic philosophy is that a high quality geologic data base is necessary and should be complete, clear, standardized, neat, quantitative, and readily useable. It may be multi-colored or simply black and white. Graphic, descriptive and quantitative recording of data is essential. A format for core logging is presented and discussed, as well as a mu1tiple overlay system for recording data gathered in surface mapping.

Jan 1, 1984

By B. F. Zwick

The entire production of oil in Ecuador so far has come from the Santa Elens Peninsula, Province of Guayas. Both the shallow fields of the northern and the deeper fields of the southern part of the peninsula have been in constant exploitation, though the former are of doubtful economic value. In Table I herewith, which commences with the total amounts produced by the various companies up to 1940, annual company totals are given for the succeeding years. The figures for 1944 have been partly estimated. Table 2 gives figures on casinghead gasoline. Shell Company of Ecuador (formerly known as Anglo-Saxon) has continued active exploration in the Oriente region east of the Andes, and during 1944 the Company's first wildcat well was spudded in. International Ecuadorean Petroleum Co. (formerly International Petroleum Co., Limited) has pursued an active exploration campaign since the latter part of 1939, and a drilling string was placed in operation about a year later. A second string of tools was added during 1943 and a third a few months ago. Ten wildcats, all dry, have been completed in this period, two wells are drilling at the present time and other locations are on the program. Seven of the wells thus far drilled are in the area between Guayaquil and the Santa Elena Peninsula, one up the Daule River beyond Balzar, one on Puna Island in the Guayas Estuary and one in the northern province of Esmeraldas. Both the present drilling wells are in the Guayaquil-Santa Elena zone. The situation in regard to concessions has changed during the past four years because I.E.P.C. has made its selections from the extensive Daule-Guayas Study Concession, as a result of which large tracts were returned to the Government; because of the expropriation of the holdings of the "Ecuapetrol," a German concern whose acreage has passed into other hands; the Peruvian-Ecuadorean boundary settlement, which has reduced Shell's holdings somewhat; and the transfer of most of the holdings of the Cia. Minero-Petrolera del Pacifico to I.E.P,C. The greater part

Jan 1, 1945

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By W. H. Herrnstein, F. H. Beck, M. G. Fontana

Sulfur solubility in a iron was measured in the 750 to 890°C temperature range and was found to be insensitive to ferrite purity within a limited composition range. The permeability of sulfur in ferrite was determined from the internal sulfidation of Fe-Mn alloys. From the solubility and permeability results, the diffusivity of sulfur in ferrite could be calculated. These results are summarized as follows: Dissolved sulfur decreased the lattice parameter of ferrite. The effect of dissolved sulfur on the tensile properties of ferrite at low temperatures was also determined. SINCE sulfur is an important residual impurity in commercial irons and steels, effects associated with the presence of sulfur as a solute in iron are of considerable practical interest. Unfortunately, certain basic information relative to the Fe-S system appears to be lacking in the literature, e.g., the effect of dissolved sulfur on the lattice parameter and mechanical properties of ferrite. In addition, discrepancies exist in previously reported results for the solubility of sulfur in ferrite. These discrepancies raise questions regarding the sensitivity of sulfur solubility to the purity and microstructure of iron. This study was undertaken primarily in an effort to obtain reliable data on the solubility of sulfur in ferrite. Additional objectives included determination of the permeability and diffusivity of sulfur in ferrite by the internal sulfidation method and determination of the effect of dissolved sulfur on the lattice parameter and tensile properties of ferrite. EXPERIMENTAL METHOD Three grades of iron, encompassing a range of impurity levels, were employed in the study. The grades were designated VME (vacuum-melted electrolytic), SPZR (single-pass zone-refined), and MPZR (multipass zone-refined). The composition of each grade is given in Table I. Poly crystalline and single-crystal strip specimens were employed in the solubility experiments. Uniform grain size strip (ASTM 3 to 5) of 0.005 to 0.020 in. thickness was obtained by alternate cold reductions of 60 thickness 60 to 80 pct and recrystallization at 650°C for i hr in pure, dry argon. Single-crystal specimens were produced in 0.010-in.-thick SPZR iron strip by the strain-gradient anneal technique. Recrystallized strip 0.25 in. wide was strained until a Luders band or bands had propagated over the length of the strip; the strip was then annealed by drawing it through a 150°C per in. gradient (890°C peak temperature) at 1 in. per hr in an atmosphere of pure, dry argon. Laue photographs of the crystals produced exhibited no discernible asterism. Specimens were equilibrated with H-H, atmospheres at temperatures between 750" and 890" by one of two methods, each of which makes use of the reaction: The encapsulation sulfurization method was employed in the majority of the solubility experiments. A strip

Jan 1, 1969

By H. R. Thresh, A. F. Crawley

THIS paper reports the results of viscosity measurements on cadmium and indium undertaken as part of a continuing program of liquid metals research at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. For several years this work has continued with support from the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. In the literature, existing viscosity data for cadmium are conflicting and for indium are scarce. To achieve reliable viscosity values, further work was deemed desirable. Viscosities were measured using an absolute technique applied to an oscillating closed right cylinder of liquid metal. The apparatus, constructed in this laboratory, and the techniques involved in its use have been described in an earlier paper.' In calculating viscosity coefficients from the experimental data. Roscoe's2 mathematical analysis was used. Because accurate viscosity determinations are dependent on accurate density data, and since the available data in the literature are conflicting, the densities of liquid cadmium and indium were also determined in this laboratory by a pycnometric technique. This increased the control exercised over all the variables contributing to the accuracy of viscosity measurements. For both density and viscosity determinations, cadmium and indium of 99.999 pct purity were used. These materials were obtained from Cominco Ltd. In order to suppress excessive evaporation losses and help prevent oxidation, a technique developed in measuring the viscosity of zinc' was used for cadmium. This involved maintaining an atmosphere of purified hydrogen in the viscosimeter during the rela- tively long periods while the experimental temperature was changed and stabilized between individual determinations of the logarithmic decrement. Then, immediately prior to a decrement measurement. the viscosimeter was rapidly evacuated to a pressure of about 2 X 10-6 torr. On the other hand. with indium. no difficulties arise from vaporization or oxidation. In this case. therefore. the apparatus was held under a constant vacuum of about 2 x 10-6 torr. When all sources of random and systematic error have been evaluated, the technique is considered to yield data accurate within 10.5 pct. The viscosity of cadmium was measured to a maximum temperature of 451.8°C and that of indium to 346.5°C. These temperatures are. respectively. 130° and 190°C above the melting points. Two separate runs were made on indium. The results are given in Table I and, when plotted. yield the smooth curves evident in Figs. 1 and 2. Values of A and C to fit the well-known Andrade1 equation were determined by a regression analysis. The equation is: where n = coefficient of viscosity. i = specific volume. T = temperature in °K Despite its empirical nature. Andrade's equation has been shown by many workers to describe accurately the temperature dependence of viscosity. During the current research program, this equation has been found to fit the data precisely for all the metals and alloys that have been studied.5,6 The A and C' values for cadmium and indium are given in Table 11. Comparing the magnitude of the present data with those of previous workers,7-10 as has been done in Fig. 1, it is evident that the results of Fisher and Phillips10 deviate markedly from the rest. With the exception of one point from Gering and Sauerwald,7 all other data agree within ±2.5 pct. However, the agreement between the present results and the work of Menz and sauerwald9 is especially good over the entire experimental temperature range. Such agreement may be expected since Menz and Sauerwald's

Jan 1, 1970

By Ellis Clark

During the winter of 1877-78 the Glendon Iron Company, by the advice of the superintendent, Mr. Frank Firmstone, decided to make the experiment of exploding a heavy blast of gunpowder in their limestone quarry at Cedar Hill, Palmer Township, Northampton County, Pennsylvania. The amount of limestone used in the five furnaces of the company is about 60,000 tons per annum, and it was thought that with successful results? this entire amount or more would be thrown down at a single operation, disintegrating the mass to a greater or less extent, and obviating the necessity of blasting and boring the rock from the face of the cliff, both of which operations are slow, and therefore, costly. The rock at the quarry is Auroral limestoue, or No. 2 of the old Survey. No fossils have ever been found in the quarry, nor in the immediate vicinity. The nature of the rock varies considerably in

Jan 1, 1879

By R. W. Raymond

There is apparently no end to the doubts, inconsistencies and absurdities in which the courts of our mining States and Territories are involved in their attempts to apply to conditions of ever-increasing complexity the provisions of our anomalous mining law. In previous papers, I have called this statute " the law of the apex," because it based upon that vague, novel and mysterious condition the most important grant of title. But the apex is scarcely a more essential feature than the end-lines and the side-lines; for the rights which it may confer may be limited in various ways by these; so that we have, in many a case, the most ridiculous result that the United States, in return for the money of a citizen, conveys to him with much solemnity, under its broad seal, nobody knows what, bounded nobody can tell how. A decision recently made at Butte by Judge De Wolfe, of the United States District Court of Montana, in the case of King et al. vs. The Amy and Silversmith Mining Company, furnishes a fresh illustration of this criticism. The diagram on the following page, constructed without precise regard to courses and distances, simply to assist in the statement of the essential features of the case, will, 1 hope, make clear the principles . involved : The plaintiff occupies a location (the Nonconsolidated) adjoining on the north the defendant's location, a b c d (the Amy), and the disputed mining-ground lies, let us say, in depth under the point W, that is, on the dip of the vein, VD, but not under the surfacelocation, a b c d. The defendant has the prior title, and claims this ground under its extra-lateral right. It is admitted that the apex does not cross the end-line, a d, and does cross the side-line, a b. Whether it crosses, at the other end of the location, the end-line, b c

Jan 1, 1889

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By A. L. Holley

The members of the society are doubtless aware that the production of American Bessemer steel works is constantly increasing; that the same converters and machinery are doing more work every year. This enlarged output is due to various causes, chiefly the following: 1st. Better organization—better knowledge on the part of both managers and men, of the plant and the process; of the way to economize the more exhausting labor, and of the arrangement of the details of labor and operations so that they shall not conflict; also, more pluck—a greater willingness to take risks, or, more properly, such an intimate knowledge of the nature and capacities of the refractory linings in various stages of disrepair, and the probable be- . havior of the fluid metal at various stages of its treatment, that the precise nature of the risk may be better known, so that the works may be crowded to their full capacity. In the early practice, after getting four or five consecutive heats in a day, the men preferred to " let well enough alone," and to devote the remaining time to preparation for another turn. Now, thirty, and sometimes forty heats are regularly made during the twenty-four hours, day after day, without the frequent occurrence and without the fear of breakdowns or " messes," as the spilling of steel charges was graphically named in Sheffield. 2d. Although no new refractory materials have been developed, improved means of preparing such as we have, and of imbedding