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By F. O. Jones

The capabilities of small proportions of divalent cations, such as calcium or magnesium, for controlling clay blocking are reported. Potentially sensitive formations can be exposed to fresh water if at least one-tenth of the salts dissolved in both the native water and invading fresh water are calcium and magnesium salts. Often, even less suffices. The behavior evidently depends upon the cation exchange properties of the clays, which favor adsorption of calcium and magnesium over sodium. Clays having sufficient adsorbed calcium and magnesium resist dispersion by water and consequent blocking of permeability. An allied phenomenon, the dependency of clay blocking on salinity contrast, is also reported. Abrupt change from highly saline to fresh water can cause blocking which may not occur if salinity is lowered slowly. A process related to osmosis is thought responsible for this behavior. Applications of findings to drilling, fracturing and water flooding are discussed. INTRODUCTION Many formations, when exposed to fresh water, can lose permeability through clay effects.',' For example, drilling-mud filtrate can cause oil permeability decreases, which persist long enough to interfere with drill-stem testing and well completion.3 Ultimate productivity may suffer when clay damage is severe, especially if drawdown pressures are low.' The injection pressures and the time required for water flooding can increase if clay blocking occurs. Earlier work indicates that clay blocking is caused by obstruction of flow channels by clays or other mineral fines dispersed by fresh water.'!" It is well known that increasing salt concentrations in water tends to prevent clay blocking. Also it is well established, although perhaps not as widely known, that the nature of the dissolved solids is also important. If, for instance, formation clays are exposed to calcium chloride solution and then exposed to weaker solutions of calcium chloride or distilled water, considerably less permeability damage results than if the clays had been exposed instead to sodium chloride solutions. The reasons for this behavior are: (1) clays are cation-exchange, or base-exchange, materials similar in this respect to zeolites or exchange resins, and (2) clays in the calcium form do not disperse easily in fresh water, whereas clays in the sodium form do. The base-exchange form of a clay is easily altered by flowing a solution through it. For example, a sodium clay can be changed to a calcium clay simply by passing a calcium chloride solution through the clay bed. There is general agreement that the reason calcium and magnesium clays do not disperse easily in fresh water is because the calcium ions do not ionize easily from the clay surfaces.' Sodium clays, however, are believed to allow the sodium ions to ionize from the clay particle surfaces. In fresh water, this allows the particle to accumulate a net negative electrical charge great enough for the particles to repel one another and, therefore, disperse more easily. The foregoing suggests that, even in the presence of a large excess of sodium, a relatively small ratio of divalent cation, such as calcium or magnesium, might serve to prevent clay dispersion. The divalent ion probably adsorbs to a disproportionately large extent, because of being adsorbed more tightly, with the result that the proportion of divalent cation on the exchange positions of the clay might then be great enough for the clays to resist dispersion. Consequently, an investigation was conducted to find how mixtures of salts in solution influence clay blocking. APPARATUS AND PROCEDURE Water permeability tests were conducted using conventional techniques. The equipment is illustrated schematically in Fig. 1. Flow rates of solutions driven through small core samples at known temperatures and pressures were measured. Regulated compressed air, usually at 10 to 15 psig, was used to drive the solutions. Core samples 0.75 in. in diameter and 1 in. long were used for the most part. Cores were saturated by evacuating and then admitting a de-aerated solution. Tight core samples were first saturated with carbon dioxide gas and then evacuated and saturated with the test solution. After saturation, 140 psig pressure was imposed for several hours. Cores were tested to insure absence of gas saturation by a Boyle's

Jan 1, 1965

By Ray Arms

This paper includes a brief classification of dry-cleaning devices, with a theoretical discussion of the principles involved. It outlines the methods of handling dust and screening difficulties at the McComas plant, as well as other plants that are being constructed and other dry-cleaning devices being developed. It describes the American Pneumatic Separator and discusses the sizing required, the effect of moisture in the raw coal, disposition of the middlings, and other aspects of the process. It gives s results of tests on various coals, and results of operation at Raton and McComas. DRY CLEANING, or pneumatic separation, is not, strictly speaking, a recent discovery. Among the archives of the Patent Office may be found many patents dating back as far as 1850 which cover early attempts to separate materials of varying specific gravity or of different shape by means of air. Hundreds of patents covering this art have been issued, which may be roughly classified into four general groups, as follows: 1. Stationary devices with pulsating air currents. The separating surface is usually riffled and air is supplied by bellows or compressors. This group' also includes air jigs, which have been used rather extensively. 2. Stationary devices with continuous air currents. These submitted the material to a continuous current of air, either horizontal or vertical. Chaff is blown from wheat by such a device. 3. Reciprocating or vibrating devices with pulsating air. A small group in which the pulsating air is supplied by bellows and some motion provided in the separating surface to move the stratified material to various discharge points. 4. Reciprocating or vibrating devices with continuous air supply. This is by far the most important group and all recent developments have been along this line. All of the above groups involve the stratification of material by air and include none of the dry methods that use other principles, such as coefficient of friction, magnetism, etc.

Jan 3, 1924

By Horace C. Porter

Most of the bituminous and semibituminous coals of this country will coke, and all of them yield, on carbonizing, more or less marketable gas and byproducts. We need, however, a finer distinction as between various grades of coking coals and between coals of different degrees of byproduct and gas-making possibilities. There is required by the consumer or the coal producer a dependable test to show whether a certain coal or mixture of coals will make coke of good commercial value for blast-furnace, foundry, water-gas, or domestic use; whether any difficulties in operation may arise from properties inherent in the coal; and whether gas and byproducts may be expected of good quality and in profitable quantity. For determining coke quality, the most dependable test is an actual run in an oven, but for byproducts a coal may better and more accurately be tested in the laboratory or in a miniature oven or retort. As to what are the most desirable qualities in blast-furnace coke, the furnace men themselves are not in complete agreement. Some desire a hard, well-burned, "hot" coke, and others get better results from a llgreener," less hardened product that burns somewhat more readily in the furnace. But certain qualities of cell structure and porosity are commonly agreed upon as desirable. Information as to what kind of coke a certain coal may be made to yield is valuable in advance, whatever may be the consumer's ideas as to the particular kind most suitable to his needs. The question arises, Can we predict coking quality with any degree of satisfaction from a small-scale test? It used to be said that coals could not be tested satisfactorily on a laboratory scale either for the coke they would yield or the byproducts. On account of the mystery with which the coking quality of coal has been shrouded and the large determining influences that many believe are exerted by mass, pressure, and the passage of carbonaceous volatile matter through the coking material, it has seemed difficult to reproduce in the laboratory the exact conditions of commercial practice. Great progress, however, has been made in recent years in elucidating the process of carbonization and many of the factors that make for the formation of high-grade coke and the recovery of the best

Jan 1, 1920

By C. P. Fiske

THE pottery of the New Jersey Zinc Co. (of Pa.) is equipped to make three classes of refractories; namely, spelter vessels, spelter condensers; and high-grade fire-brick. The most important of these are the spelter vessels, on account of the extreme severity of the service which they must perform, necessitating great care in the selection of materials and in the whole process of manufacture. Next to the spelter vessels in importance? come the condensers, as large numbers are used in the manufacture of spelter, and improvements m quality result in material decreases in working cost. , While the fire-brick which form the laboratory, or high-temperature portion of the spelter furnaces, are placed at the foot of the list, they-are nevertheless of much importance, since high quality will decrease the frequency of the always expensive shutdowns for repairs. To promote simplicity, the manufacture of these three products will be described separately in this paper, except in so far as materials and the crushing and handling system common to all are concerned. Materials Bond Clay.-The bond clay used entirely at the Palmerton pottery is a St. Louis clay furnished by the Grand View Fire Clay Co. It is stored in a system of covered bins, and no attempt is made to weather -it in the, accepted sense of the term " weathering." Some years ago our clay was weathered before pugging, but we did not find the benefit sufficient to offset the additional handling and the loss. of clay incurred. Furthermore, we believe that the rotting of the pugged mix (described later), accomplishes the same results to better advantage. That there is some action taking place in the clay while stored in the covered bins, however, is, evidenced by an increase in volume which at times has caused damage to the retaining walls of the bins. We have at present a stock of bond clay weathering in the open, and when this is put into service an opportunity will be afforded for making comparisons-with the clay as usually handled.

Jan 10, 1917

By AIME

VERSATILITY is perhaps the outstanding characteristic of the subject of this sketch. He is author, golf-player, musician, public speaker, philatelist, German scholar, and has been a school teacher; but these are incidental. Oliver Ralston's professional forte might be described as beneficiating solid minerals and he has dealt in an important way with practically all of them. To this work he has brought a fertile mind stimulated by keen imagination but kept on the track by a sense of economic balance. An indication of his versatility is evidenced by his career with the Bureau of Mines, which he first joined in 1912, when the Bureau was just one year old. Except for two excursions into industry-Hooker Electro Chemical Co. (1917-20) and United Verde Copper Co. (1928 to 1935)-his entire professional career has been with the Bureau.

Jan 1, 1946

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,1 and they seem, indeed, to diffract as individuals causing the Hull pattern of a, severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles determined by the manner and intensity of cold working.

Jan 1, 1927

By Philip Drinker, R. M. Thomson

In the mining and metallurgical industries, numerous problems arise requiring determinations of solid and of liquid particles suspended in air. Frequently, these problems are of local interest and involve purely economic or operating difficulties; on the other hand, toxic effects from the inhalation or the ingestion of substances suspended in air may be a matter of concern. For checking up process improvements or for determining ventilation efficiencies in problems of this general nature, various methods have been proposed. .Although simpler methods are often satisfactory, precipitation combines several desirable features that other methods lack. This paper is, therefore, devoted to a discussion of portable alternating-current precipitators applicable to the quantitat,ive determination and microscopy of dusts, fumes, and smokes in air. Small particles suspended in gases, such as air, are referred to in the literature as aerosols or suspensoids. Of these terms, suspensoids appears to be preferable as being more nearly in keeping with words in everyday use. In problems involving air pollution by small particles—by suspensoids—it is convenient to distinguish three broad classes based on the size, the degree of dispersion, and the method by which the particles become suspended in the air. Dusts.—Particles or aggregates of particles, 150 to 1 micron in diameter, that are thrown into the air by mechanical agencies are termed dusts. Examples are silica; talc; cement; organic dusts such as hard rubber, starch, and cocoa; flocculated fume, and smoke products. Fumes.—Particles, 0.2 to 1 micron in diameter, formed from chemical or physicochemical reactions are known as fumes. Examples are ammonium chloride, lead and mercury, zinc and magnesium oxides, fogs, and acid mists. Smokes.—Particles, less than 0.3 micron in diameter, formed by incomplete combustion of carbonaceous and other substances are called smokes. Examples are the particles formed from burning tobacco, oil, tar, and gas.

Jan 1, 1925

By C. G. Dunn, P. K. Koh

THE primary recrystallization texture in cold-rolled silicon iron, which is the matrix texture for developing the Goss texture or the cube-on-edge texture by secondary recrystallization at temperatures near 900°C,1-5,21 has not been adequately described. Thus from the present available information, it is not possible to explain satisfactorily both the grain-growth selectivity of the matrix and the often observed magnetic torque curve, which itself provides some information on the texture. Also lacking is information on the special annealing texture that develops in this material when the annealing temperature is 1200°C or higher and the rate of rise to temperature is extremely rapid. From the work of May and Turnbull5 and from unpublished work, it was known that isothermal annealing near 1200°C tends to reduce the extent of secondary recrystallization and that a much weaker cube-on-edge texture results if appreciable normal grain growth replaces secondary recrystallization. Koh and Dunn6,7 have obtained additional information on complex primary recrystallization textures from further studies made after normal grain growth. In these instances the initial textures were retained during normal grain growth. A similar result reasonably could be expected in the present study except for the presence of a grain growth ihibitor1-5,8,9.21 and its tendency to allow only a few grains to grow. However, any information on the orientations of grains in the special annealing texture, even if far from representative of the initial matrix texture, would provide useful information on the nature of the matrix texture. In the present texture study the method of Newkirk and Bruce,10 which is based on the methods of Geisler" and Schwartz, 12 is used to obtain a complete (110) pole figure of the primary recrystallization texture. The high-temperature annealing texture is determined simply from the orientations of a large number of selected grains. The kinetic nature of the process that produces the annealing texture is treated elsewhere13 and it is shown that a form of secondary recrystallization with a very high rate of nucleation occurs during rapid annealing at high temperatures. EXPERIMENTAL PROCEDURE Commercial 0.014-in. cold-rolled silicon iron strip (3.16 wt pct Si), prepared by two stages of cold rolling with an intermediate short anneal, was given a decarburizing 3-min anneal at 800°C. Me-tallographic studies indicated complete recrystallization. Short-time anneals at 900° C and at higher temperatures proved that secondary recrystallization had not begun at 800°C, in fact, the short additional anneals were still in the induction period of secondary recrystallization. A rapid rise to an annealing temperature of 1260°C (2300°F) was obtained in a BaC12and NaCl fused salt bath. The structures that resulted from anneals in the range 12- to 1000-sec duration were relatively finegrained, even though the growth was a form of exaggerated grain growth13 or secondary recrystallization with a high nucleation frequency.= Many of the grains were large enough for an X-ray study using a 5-mil X-ray beam. A transmission Laue Camera and an optical-mechanical stage for moving the grains into the X-ray beam were used. A total of 325 grains were X-rayed in this manner and the grain orientations determined. Complete (110) pole figures were obtained for the primary recrystallization texture using CoKa radiation at 30 kv in the back-reflection range, such as (220) for (110) poles, as described recently by Newkirk and Bruce.10 The low voltage serves to reduce the spurious white radiation to a minimum. A filter of 0.001-inch iron foil was located in front of the detector slit for transmission and in front of the beam slit for back reflection. A new and improved specimen holder extended the useful tilting angle range for transmission to 70 deg instead of 60 deg as previously reported.' A torque magnetometer was used to obtain the magnetic torque curves for a number of l-in. diam disk specimens. RESULTS The (110) pole figure of the material after recrystallization at 800°C is shown in Fig. 1. The positions of the pole concentrations are found to be

Jan 1, 1961

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By Philip M. Mc Kenna

When a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be considered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essential wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered. Hardness has been the property of greatest practical interest in tool materials. The word "hardness" is a generalized term lacking definite-ness unless the specific test used is described. However, efforts to explain physical properties as a consequence of chemical bond, and distance between atoms in chemical compounds have been illuminating. This seems the most generalized attack on the problem, and is based upon the idea that atoms in a lattice are held together as the square of the valence and inversely as the square of the distance between the atoms. The compounds compared must all be of the same crystalline arrangement. 100 W2 It is interesting to note the values of the figure 7 A 3 /3for a number of

Jan 1, 1938

By Philip M. Mc Kenna

When a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be considered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essential wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered. Hardness has been the property of greatest practical interest in tool materials. The word "hardness" is a generalized term lacking definite-ness unless the specific test used is described. However, efforts to explain physical properties as a consequence of chemical bond, and distance between atoms in chemical compounds have been illuminating. This seems the most generalized attack on the problem, and is based upon the idea that atoms in a lattice are held together as the square of the valence and inversely as the square of the distance between the atoms. The compounds compared must all be of the same crystalline arrangement. 100 W2 It is interesting to note the values of the figure 7 A 3 /3for a number of

Jan 1, 1938

By M. Friedman

Applications of rock mechanics to the design of engineering structures in rock involve the assumption that the stresses are due entirely to the present applied loads. For instance, it is assumed that the vertical normal stress in undisturbed rock free of topographic effects is equal to the weight per unit area of the overburden. In fact, vertical dilatational strains associated with stresses of more than 100 times the present overburden pressure have been measured by strain-relief methods on outcrops. 1,2 The notion of residual strain (stress) or latent stress3 seems unassailable; and indeed this has long been recognized by metallurgists. It is difficult, however, to assess the residual component of the in-situ state of elastic strain with conventional strain relief methods employed in mines or down boreholes. That is, in principle, the in-situ state results from the superposition of present applied loads (natural or man- induced) and potentially recoverable elastic strains (stresses) that exist in a given volume of material even though there are no external forces across the boundaries of the body (Voight,4 and Fig, 1). Accordingly, only in unloaded blocks can the true residual strains be measured by strain relief methods. Using X-rays, the elastic strains locked within the quartz grains or crystals of a rock can be measured. These strains are known to persist even when the rock is reduced to small chips but to vanish when the rock is disaggregated and the grains are powdered. Although we have just begun to investigate the mechanisms by which the strains are stored (see Preliminary Results), we believe that "pressure solution'' at grain boundaries, secondary cementation under load, permanent ("plastic") deformation, and temperature changes are possible processes. In any event, in our study of naturally deformed rocks, it is significant that we are work-

Jan 1, 1972

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.' When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg' lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962

By A. W. Hesse

VENTILATION of all types of coal mines is fundamentally the same, in that sufficient air must be provided to properly dilute and remove dangerous and obnoxious gases and leave the oxygen content of the air not under 19 per cent in all places where men and animals must work. Perhaps animals should not be mentioned, as the speed of mechanical loading leaves livestock behind and outmoded. Since this paper has to do with the influence of mechanical loading equipment on ventilation, the problems will be confined to the splits and the coal-producing places of the mine. The removal of coal dust from the air, or its rapid transmission to the return air courses; the possible increase in the liberation of gases by the multiplication of cuts in the coal made during one shift or multiple shifts; and the additional electrical equipment at the faces, are the factors that cause the added importance to good ventilation in the permissible equipment area of gassy bituminous coal mines. VENTILATION FOR MECHANICAL LOADING IN GASSY MINES In gassy mines, the air currents must be maintained across the faces in such a way as to prevent short cuts to the returns and leaving pockets in which accumulation of gas might occur. To do this, two or more doors are required on almost every entry containing a track to the face, so located that in no event will a trip of cars block open the doors and permit the air to by-pass some place or places on the air-approach side. This method frequently requires the use of unusual lengths of duplex cables to reach the mechanical equipment at the faces, particularly where the distances between parallel working places are 100 ft., as at the Nemacolin mine. Fig. I shows a pillar section being worked with mechanical loaders. This layout requires carrying the air in on the right and releasing it on the left, because the track clearance is on the right side and the line brattice is built on this side from the last crosscut to the face. Thus, the air travels to the face with greater velocity, and gives more assurance of sweeping out the gas that might be exuding from the crevices of the coal. All working places, in driving through solid coal, are thus treated alike. They are all potentially gassy and must be swept clear of whatever may contaminate the air. Once the air starts into the working section, it is not released until it does a good job. Of course the volume of air must be large enough not only to dilute the gases but to carry away explosive fumes and fine coal dust quickly. Mechanical loading entails cutting and drilling of the coal during the same working period as the loading when two-shift and three-shift operations are employed, and all three processes create finely pulverized coal, which in itself is hazardous if not controlled by some means. If the ventilation is inadequate and gas accumulates, and a spark from defective electrical

Jan 1, 1941

By Robert R. Abbott

The influence of various elements in retarding or accelerating the absorption of carbon during the process of carburization is fairly well known. In general those elements which form carbides accelerate the absorption, while those which do not retard it. It has sometimes been wrongly stated that those elements which raise the temperature of the critical range increase the absorption, while those which lower this temperature decrease it. Silicon is a notable exception to this rule, for its influence is to raise the critical range but to lower the absorption of carbon. Some elements which do not form carbides have no apparent influence upon the absorption rate. Carbon itself retards the absorption rate. With a view to obtaining more exact data upon the subject the following experiments were undertaken: 208 steels of different chemical composition were selected to represent most of the types of modern constructional steels. Specimens 2 in. in diameter and 9 in. in length were weighed to milligrams. They were then packed in the special carburizing box shown in Fig. 1, and kept in the furnace for 10 hours at a temperature of 900' C. A duplicate experiment was conducted at 1,000° C. At equal intervals of time the box was rotated in the furnace so that two complete revolutions were made in the 10 hours. This precaution was taken to neutralize as much as possible any effect of unequal heating. At the end of the 10 hours the box was allowed to cool in the furnace with the doors open. The specimens were then weighed again and the increased weight (carbon) determined. In the following table are given the analyses of the various steels, together with the increased weight of carbon expressed in milligrams.

Jan 1, 1914

By E. W. Schilling

THE-separation of hematite by hysteretic repulsion was first brought to the attention of the public in 1922, by W. M. Mordey1. Three-years later another paper2 was published and after another four years a third paper3 appeared in the South African publications. Certain data were lacking in these papers. In order to continue the work intelligently a knowledge of the shapes of the hysteresis curves for certain minerals was very necessary. This information was not available until the present year4. It was known that reduction of certain ores rendered them amenable to this process of separation but definite data in. the form of curves showing exactly the effect of such treatment were lacking. Prob-ably our best source of information on the separation of minerals by the use of alternating-current magnetic fields today is the reports from the U. S. Bureau of Mines 5-7. It is not the purpose of this paper to tell the reader in detail how to make a commercial separator. Experimental models have recently been made7 and the results obtained have been so good that it is the opinion of the authors that the public will soon take an active interest in the subject and its development. The writers have constructed a separator that is considerably different in construction and operation from the two types described by Mr. Davis. This will be described; but the real purpose of this paper is to outline certain experiments and give curves showing data that have a fundamental bearing upon the practical construction of a separator of this type.

Jan 1, 1936

New Jersey Zinc Co. - The Plants Canon City Palmerton Depue

Jan 12, 1953

By W. M. McKewan, R. G. Olsson

In order to improve the understanding of the iron oxide reduction mechanism, the rate of equal molar diffusion of hydrogen and water vapor was measured through disks of porous iron and alumina. The measuretneizts were made at atmospheric pressure at 800°, 900- , and 1000°C. It is shown tint the reduction of dense hematite pellets with hydrogen at these temperatures and at atmospheric pressure is to a great extent limited by gaseous diffusion between the bulk-gas phase and the iron-wustile interface. THE investigation of the reduction of iron oxides with hydrogen has been the subject of numerous papers. Although the effects of temperature, pressure, and gas composition on the rate of iron oxide reduction have been studied, the actual mechanism of the reduction process has not been definitely determined. As a means of improving the understanding of the mechanism, the rate of equal molar counterdiffusion of hydrogen and water vapor was measured through porous iron and porous alumina disks at reduction temperatures. The alumina was used as a basis of compari-son because its pore structure is homogeneous and independent of temperature. The porous iron was prepared by the reduction of dense hematite disks with hydrogen at the temperature of the subsequent diffusion experiment. The hematite disks were made from pellets that were identical to those used by McKewan1,2 in his study of iron oxide reduction with hydrogen. In these investigations the weight loss and rate of movement of the various interfaces were measured as a function of the reduction temperature and gas composition. With these reduction data and the presently reported diffusion data it is possible to determine the importance of H2-H2O transport between the bulk-gas phase and the Fe/FeO interface to the reduction of dense hematite. APPARATUS AND PROCEDURE A porous iron or alumina sample was held in the base plate of a sealed canister containing porous granular wustite, as illustrated schematically in Fig. 1. The canister was suspended from an automatic recording balance in a vertical tube furnace through which flowed hydrogen and water-vapor mixtures of known composition at atmospheric pressure (0.96 atm). Hydrogen from the gas stream diffused through the porous sample, reducing the wustite in the interior of the canister. The water vapor that was formed diffused back to the gas stream. The rate of diffusion was determined from the recorded weightloss data. The furnace, automatic balance, and gas-metering equipment have been described previously.2 The main body of the canister and the tubing extension were made of stainless steel while the base plate was made of high-purity iron. The main body of the canister was % in. in diam. It held approximately 6 g of porous granular wustite that was prepared by reducing 0.1- to 0.2-cm-diam specular hematite particles at 900°C with an H2-H2O mixture of a composition near the iron-wustite equilibrium value. The upper end of the 1/8-in.-diam tubing extension was sealed with a segment of plastic tubing and a tubing clamp. The temperature at the top of the furnace was sufficiently high so that no water vapor condensed inside the extension. In the experiments with porous iron, iron oxide samples were prepared from reagent-grade hematite that was pressed and sintered in a manner previously described.' The resulting pellets had a density of 5.15 ± 0.05 g per cu cm. Each pellet was centerless-ground

Jan 1, 1967

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

By L. C. De Jong, J. F. Shirley, M. L. Campbell

The Toquepala concentrator of the Southern Peru Copper Corp., located approximately 720 miles southeast of Lima near the Chilean border, processes 36,500 tons of ore daily containing between 0.50% and 3.00% copper. The molybdenite content in the ore also varies greatly, ranging from essentially nothing to as high as 0.15%. The 1966 yearly averages were approximately 1.20% copper and 0.03 % molybdenite. The three basic problems that plague the opera- tion of any molybdenite recovery plant are all present at Toquepala in large measures. Both the quantity of plant feed and the quantity of molybdenite contained in the plant feed are continuously changing. Even more detrimental to an efficient operation is the fact that the copper mineralization in the feed frequently changes once in every 24 hours and occasionally once a shift. From the point of view of the molybdenite plant metallurgist, there are four distinctive chalcopyrite concentrates and, at least, an equal number of chalcocite concentrates treated in the molybdenite recovery circuit. The various types of concentrates are distinguished mainly by their mineral content and how effectively the copper minerals are depressed by the different reagents used in the circuit.

Jan 9, 1967