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By John W. Vanderwilt

The unpredictable behavior of ground movement and subsidence has complicated the problems that attend the extraction of large quantities of ore. Special studies, particularly relating to coal mining, have yielded such a voluminous literature and so many involved controversial theories that a partial review would be difficult. Limited space makes any kind of a review impractical. The features to be considered cover only a relatively small part of the broad problems of ground movement and subsidence, but it is believed that this small part is critical. The practical aspects are important, since they bear directly on safety of mine workings, on recovery of ore and on dilution of ore in block caving and related systems for extracting large quantities of rock. The ground movement to be described occurs outside the vertical boundaries of a caved block in the area that is commonly referred to as being in the "zone of draw." "Draw" is a term that originated in the subsidence problems related to coal mining, and it is defined by a line drawn from the margin of the area caved underground to the most distant fracture at surface on the same side of the caved area as shown in Fig. I.' A line thus drawn is called the cave line, and its angle with respect to the horizontal is the cave angle or angle of draw. It is understood that the line is taken normal to the limit of mining, and in a vertical plane. The prevailing theories as to draw and angle of draw assume that appreciable movement occurred along the cave line, which has been described as a fracture resulting from the shearing action brought about by the weight of the overlying load. Fig. 3 shows diagrammatically the mechanics of ground movement adjacent to an area of subsidence according to the prevailing theory of draw (A, from Royce2) and, for comparison, ground movement observed in the Climax mine (B). The text in Peele's Handbook2 referring to Fig. 2 does not state the meaning of the "original position of top of workable ore" in the rectangular space above "ore in place," and the arrows are not explained. However, this presentation is most concerned with the zones outside the rectangle. According to the prevailing theory, as shown at the extreme left under A, Fig. 2, the vertical tension cracks at surface change at a shallow depth to shear fractures forming the cave line, and it is assumed that appreciable movement takes place along the cave line toward and into the subsiding caved block. The mechanics of ground movement observed in the Climax mine, as shown under B, Fig. 2, does not accord with the prevailing theory, particularly as regards the cave angle and draw. The vertical tension cracks seen at surface die out at depths of 150 to 225 ft. and shear fractures do not develop. Movement is confined at surface to a mantle of rock 50 to roo ft.

Jan 1, 1949

By M. B. Willey

The Louisiana Continental Shelf is a submarine area extending offshore as much as one hundred miles. The Gulf bottom in this region varies considerably in extent, profile and composition and consists largely of sedimentary deposits, predominantly those of the Mississippi River. It is very young in a geological sense. Up to the present time few major structures have been erected offshore in the Gulf and no comprehensive preliminary tests have been carried out. Results of pile driving tests are of little value as actual bearing capacities far exceed the dynamic resistance to driving as measured by conventional formulas. Soils encountered are, with few exceptions, cohesive and piling consequently develop their supporting power through surface friction. Because of the time required and relatively high costs, no complete load tests have been made. The results of those tests which have been made, and information obtained from pulling piling in one structure, indicate that design loadings could be considerably increased, and it is contended that comprehensive preliminary investigations including an actual load test, combined with borings and examination of materials encountered by competent soil experts, would effect economies in design far in excess of their cost. The Louisiana Continental Shelf—General The Louisiana . . . continental shelf is a submarine area which extends seaward for as great a distance as one hundred miles off the present shoreline. The Gulf bottom in this region is characterized by low slopes and its outer margin is outlined by the fifty fathom (300 ft.) contour. South of the margin of the shelf the slopes steepen abruptly in the continental slope zone and plunge into the deeps of the Gulf of Mexico.l The engineer who is called upon to design a structure on this shelf is concerned only with the uppermost portion to a depth generally not to exceed Ioo to 150 ft. This layer is very young in a geological sense, and it has the characteristics usually associated with infancy. A few of these are lack of strength, lack of uniformity, and high water content. It consists of the sedimentary deposits of the various rivers and streams entering the Gulf. These streams are all heavily burdened in quantities sufficient to fill the areas at their mouths, were it not for the fact that continual subsidence, equal or greater in amount and acting directly opposite, prevail over the sedimentary workings of the streams. This subsidence has been estimated by geologists to be at the rate of at least one foot per century. Influence of Mississippi River The Mississippi River, which has been the predominant factor in the formation of practically all the Louisiana continental shelf, is one of two rivers flowing into the Gulf that have been able to build protruding deltas. The Mississippi has done so because of its enormous size and load. It deposits sediments in amounts sufficient to replace and actually gain on the amount of subsidence.

Jan 1, 1949

Discussion of the paper of HOWARD N. EAVENSON, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October,' 1914, pp. 2637 to 2660. GEORGE S. RICE, Pittsburgh, Pa.-I think it is very wise to point out the greater liability to explosions in certain parts of the year, if there be such difference, with the caution, however, that vigilance be not relaxed at other times. In comparing the figures for the United States with those of Europe, I think we should separate them as far as possible according to cause of origin and means of propagation. That is to say, it would appear to me that the majority of our explosions are due more directly to the ignition of coal dust directly from the flame of explosives, whereas, judging from my inquiries and observations in some of the mines of Europe, the majority of their explosions have been caused by the ignition of fire damp. Now, in the case of fire damp, I do not think that anybody has yet attempted or has been able to find any connection between the seasons and the issuance of methane into mines. One thing must be borne in mind, that if you get a strong explosion of fire damp, dust of a character that might not ignite readily by itself might assist in the extension of an explosion of fire damp through a considerable area in the mine, if not throughout the mine. While it is true we have many lesser explosions in this country attributable to fire damp, it would appear that the majority of all the mine explosions of the country, in considering the means of propagation beyond the locality of the origin, are due to coal dust; and it is the liability to coal-dust explosions that appears to be affected by seasonal changes. Hence the desirability of separating statistically (if it could be done by the inspectors) fire-damp explosions from coal-dust explosions, in order to obtain the true value of the seasonal effect. Nevertheless, in spite of the inclusion of fire-damp explosions with coal-dust explosions, the preponderance of the evidence, as indicated in Mr. Eavenson's figures for American mines, has shown that' in this country there were more explosions in the winter and spring months, when the mines are drier; that is, when the mines are apt to be drier. Whereas, according to the European figures that he has gathered, it seems to be very clearly demonstrated that in France, England, and Belgium, the time when explosions occur has no connection with any particular season. That, I think, is partly due to the point just mentioned, that a majority of their explosions have originated from fire damp. The European mining men have been more careful, generally speaking, with the use of explosives than we have, so that the cause of ignition from that source has been less. Only comparatively few of the mines in foreign

Jan 4, 1915

By J. H Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By G. W. Jones, G. S. Scott

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By F. W. Rols-Hausen, F. W. Jessen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By W. Hurst, A. F. van Everdingen

A distillate-bearing sand complex is often made up of sand stringers of different permeabilities. In order to take into account the influence of the different permeabilities, "parallel flow" is defined, and this concept is used to compute the recovery efficiency of recycling such a sand complex. In the first approximation the position of the wells with respect to one another is not considered. In order to compute the effect on the recovery efficiency of the position of the wells, the area of a field is considered to be made up of rectangles; each rectangle containing one input well in the center and two producers located symmetrically with respect to the input well. Formulas are given from which to obtain the pressure and streamlines in a steady-state flow. A method is devised to compute rapidly the successive positions of the dry gas front. If the field is irregular in shape, pressure and streamlines can be obtained by a potentio-metric electrical model study. By using the concept of "parallel flow" and the results obtained by mathematical analysis or by electrical model study for a homogeneous formation, the effects of different permeabilities and of the location of the wells can be established. From these studies it is apparent that the efficiency of recycling can be profoundly influenced by differences in permeability among the various parallel strata. Introduction With the discovery of an increasing number of gas-distillate fields in the Gulf Coast, engineers have had occasion to give more thought to the performance of these reservoirs, as evidenced by the literature published in recent years. In the majority of studies published so far the formations are considered to consist of uniform, homogeneous sand. In this paper the authors wish to bring out the effect of variations in the permeability of the formations on the over-all recovery efficiency of wet gas in cycling operations. The importance of the permeability profile is clearly indicated by the fact that in gas cycling, highly permeable stringers in an otherwise tight sand can allow complete displacement of wet by dry gas in these stringers long before the wet gas in the tight portions of the sand is displaced. This by-passing will be reflected by a reduction in the condensate content of the production sooner than can be anticipated from a mathematical analysis or an electrical model study on uniform sands. Electrical model studies or mathematical analyses cannot take into consideration the manifold variations of permeability within the reservoir. Experimental as well as analytical difficulties make it necessary to consider the prototype for either of these studies as a perfectly uniform sand. Mathematical analyses are applicable only when a reservoir can be divided into units of simple geometrical form, of uniform thickness throughout. Electric model studies are capable of giving information on reservoirs of any shape or thickness, but it is essential that the sand be considered homogeneous, so that three-dimensional flow can take place. The method of approach in the following

Jan 1, 1946

By W. M. Johns

The geological mapping of Lincoln and Flathead Counties was a five-year project undertaken by the Montana Bureau of Mines and Geology. This paper, written by the Project Geologist of the survey, is primarily concerned with the stratigraphy of the Belt rocks encountered in mapping. Lincoln and Flathead Counties of northwestern Montana are underlain by sedimentary rocks of the Belt Series of Precambrian age. In only a very small part of the area, near Libby and Troy, have economic mineral deposits been worked with any success. Most of the area has been inadequately mapped as to geology. The region is crossed by the Great Northern Railway and served by the Pacific Power and Light Co.; officials of these two companies believed that with better geologic maps, prospecting might be stimulated and lead to the discovery of mineral resources that would contribute to new economic development within the area. A cooperative mapping agreement was proposed jointly by the two companies to the Montana Bureau of Mines and Geology in May 1958, and thus was born the Kootenai-Flathead five-year project. The dual objectives of this project are: 1) the possible location of mineral deposits of economic value, and 2) the ''stimulation of prospecting exploration" by others. This was to be achieved by geologic mapping of some 6800 sq miles and by establishing a field office in Kalispell where prospectors could come to have their rocks and minerals identified and receive geological advice on their problems. This writer has finished four field seasons as Project Geologist and thus became familiar with the Belt section in the Libby, Yaak River, Ural, Thompson Lakes, Pleasant Valley, and Stryker quadrangles (see Fig. 1). Progress on the project is given in annual reports issued by the Bureau.* This *Montana Bureau of Mines and Geology, Bulletins 12 (1959), 17 (1960), and 23 (1961). paper is concerned essentially with the stratigraphy of the Belt rocks so far encountered in mapping. PREVIOUS WORK IN THE AREA Willis28 made the first study of the stratigraphy and structure in the Lewis and Livingston Ranges of Glacier Park just east of the project area. In 1904, Daly made a study of the Belt rocks of the 49th parallel, using the names from bottom up, Creston, Kitchener, Moyie, and Gateway, for rocks ranging in age from that of Prichard to that of basal Missoula group. Walcott26 studied the Belt rocks exposed in the Mission Range (see Fig. 1) and other areas to the south of the area under discussion. Calkins and McDonald made a reconnaissance of northern Idaho and northwestern Montana in 1905. Calkins was the first to use Walcott's term 'Ravalli' as a group name for the strata equivalent to the Burke, Revett, and St. Regis formations (see Table I). Clapp worked on the Belt of western Montana (including Lincoln and Flathead Counties) throughout his lifetime. The Fentons9 studied the Belt of Glacier Park and

Jan 1, 1962

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:'-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290' C. c) The third stage covers the formation of ce-mentite between 290o and 400' C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By John Wulff, Robert Kamm, M. A. Steinberg

IN a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described, In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was, found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region -of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. CIRCULAR-HOLE GRIDS AND ANALYSES OF RADIOGRAPHS Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in, centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1,125 in. in diam and the clearance between plungers and die wall was 0.001 in, The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value on an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1948

By W. D. Steele, S. D. Brady

The Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains minable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon-galia Co. thence south and southwest across the state to Wayne Co. near Hunt-ington. The Pittsburgh coal is also minable in the Upper Potomac region but is now practically exhausted there. The total minable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13¼ billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio River as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern West Virginia District comprising Wetzel, Mon-ongalia, Marion, Preston, Harrison, Dodd-ridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 1880 (when the Monongahela River Railroad, now B. & 0. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgan-town and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Mononga-hela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of minable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. Economic Importance The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1949

By G. S. Scott, G. W. Jones

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By M. A. Steinberg, J. Wulff, R. Kamm

In a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described. In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. Circular-hole Grids and Analyses OF Radiographs Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in. centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1.125 in. in diam and the clearance between plungers and die wall was 0.001 in. The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value On an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1949

By C. O. Tarr, G. V. Smith, R. F. Miller

METALLURGISTS have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 2050°F.1 This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In 1935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0.1 5 per cent carbon steel that had been in senrice for about 26,000 hr. at a temperature of about 1100° to 1200°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7o0°C. (1290°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, obsenred graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 1200°F. Unstressed samples of 0.60, 0.86 and 1.14 per cent carbon steels graphitized almost completely in 360 hr. at 1200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at 1200°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from 1600°F. and by cold-working prior to annealing. In creep tests of normalized o. I 5 per cent carbon steel killed with 2.5 lb. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at 1000°F. under a stress as low as 15m lb. per sq. inch.

Jan 1, 1944