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By J. R. Campbell

IN order to discuss the subject intelligently, it will be necessary to touch briefly on the forms in which sulphur is supposed to exist in coking coal to be carbonized in beehive or byproduct ovens. Sulphur is known to exist in coal as sulphides and sulphates, as can be determined experimentally. Then there is the so-called organic sulphur, i.e., sulphur in combination with the carbon, hydrogen, and oxygen of the coal, about which much has been written, but nothing definitely proven in an experimental way. In fact, so far as we know, there never has been developed a satisfactory and conclusive method in the laboratory for the direct determination of organic sulphur. For most coking coals, it can be safely assumed that the preponderance of sulphur is in the form of pyrite (FeS2). When exposed to comparatively low temperatures during the coking process, it loses its sulphur according to the following chemical reaction: 7FeS2 = Fe7S8 + 6S. It will be seen, therefore, that six out of the 14 atoms of sulphur (or 42.8 per cent.) are expelled, or volatilized. Fe7S8 remains in the coke as pyrrhotite, or magnetic sulphide of iron; this accounts for the highly magnetic properties of the powdered coke. A more commonly accepted reaction is FeS2 = FeS + S, in which the straight sulphide of iron is produced with 50 per cent. volatilization of sulphur. In the beehive methods of coke making, air is introduced in sufficient amounts to carry on the distilling and the coking processes, and the sulphur is oxidized along with the other volatile products: First, into sulphur dioxide (SO2), known by the pungent and suffocating odoremitted from the trunnel head; second, into sulphuric anhydride (SO3); and, finally, into sulphuric acid, as it comes into contact with the air and moisture. In a properly regulated draft on a beehive oven, there is never complete combustion of the gases. In other words, the coking process should be carried on in a reducing atmosphere, and a low-grade producer gas kept issuing from the trunnel head. For coals of about 30 per cent. volatile matter, the ratio of air to gas is 3 ½ to 1. In complete combustion, the ratio is 6 to 1, producing an extremely high temperature

Jan 1, 1916

W. E. WRATHER, Wichita Falls, Tex. (written discussion*).-The appearance of Mr. Brokaw?s with-the chemical composition of "paraffin dirt" will be welcomed by oil geologists who have worked in the Gulf Coast district. It is to be hoped that it will lead to a discussion of the subject which will throw some light on the relation this peculiar substance bears to the occurrence of oil deposits. The problem of locating oil pools in advance of drilling is at the best a very intangible matter in the district along the Gulf Coast, and it is therefore desirable to make the most of any clew which may be of the least assistance to this end. Geologists have been familiar with "paraffin dirt" for a number of years, and have informally discussed its value as a surface indication of oil. But doubtless owing largely to the fact that they have been unable to define its exact composition, very little information has appeared in print on the subject. The presence of this baffling and somewhat indeterminate substance is now quite generally accepted as one of the most reliable indications of a gas seepage. The question is whether paraffin dirt necessarily indicates that the escaping gas is an emanation from an oil deposit, or whether it merely indicates that marsh gas (urethane) has here escaped from its source in "the abundant decomposing vegetation entombed in the sediments of the old Mississippi Embayment, and the Gulf Coastal Plain. The presence of this material has been relied upon to a great extent, both by oil producers and geologists, in the location of wildcat wells, since the discovery that it was associated with gas seepages. It is quite true that other surface indications were often present at such localities, but if, in addition, paraffin dirt could be found in the vicinity, this fact was accepted as the final justification for drilling a test well, despite the fact that no one seemed to understand its chemical composition or to know why it should be associated with oil. In fact, for a long time it has generally been accepted that the name is a misnomer, that very little, if any, paraffin is present in it, or, for that matter, any other known fraction of crude oil.

Jan 7, 1918

By C. O. Brawner

Introduction The procedures used to design slopes in rock have only been developed over the past 10 years. Therefore, continued review and assessment of field experience by the publication of case studies is necessary to determine the accuracy of the theory and the application of the design techniques being used. Where failures have occurred, mine management should insist that the slides be 'back analyzed' to determine the shear strength parameters at failure. These values should be used for any pit design as they reflect site conditions more accurately than any other procedure. The previous papers have dealt with the basic concepts and factors that influence stability. To illustrate the application of these concepts in the study of practical stability problems, six ease studies have been selected for review. The examples include failure of tailings dams due to an earthquake, failure and redesign of a slope in overburden, review of failures of rock slopes, calculation of the amount of seepage into a pit and influence of the groundwater on stability, and the design of slopes for a proposed 2,500 ft. deep open pit mine. All but the first example are drawn from the authors personal experience. EXAMPLE 1 Failure of Tailings Dams Due to an Earthquake On March 28. 1965 a serious earthquake occurred in Chile with the epicenter located near the town of La Liqua, about 80 miles north of Santiago. The earthquake had a rating of 7 to 7.25 on the Richter scale. A record of the acceleration was taken at Santiago where a maximum horizontal acceleration of 0.18 g. was recorded. Many small mines are located in this region. Each of the mines provided impoundment storage for tailings with one to three dykes. As a result of the earthquake, most of the dams failed. The most serious failure involved two dams at El Cobre where more than 2,700,000 cu. yd. of tailings flowed into the valley, travelled over 7 miles in a few minutes, destroyed part of the town of El Cobre and killed more than 200 people. The Chilean government commissioned an investigation into the failures. A summary of the findings was published by Dobry and Alvare7 in 1967 (1). The location of the earthquake and the tailings dams which were investigated is shown

Jan 1, 1971

By W. A. Boyer

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By Carville E. Sparks, Rollin Farmin

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By H. R. Drullard

TO obtain the best results from hammer drills, close attention must be paid to two factors in drill maintenance, which are of equal importance; one is lubrication, the other is the shank. With the exception of stoping drills, most modern rock drills require both oil and grease. The oil ports are in the lubricator, on or behind the hammer cylinder; the grease port for the lubrication of the chuck sleeve and rotating mechanism is on the chuck end. Ordinary machine oil is not adapted to rock drills; a heavier more gelatinous oil such as castor machine oil or liquid grease should be used. The lubricators should be filled once for every 12 or 14 ft. (3.5 to 4 m.) of hole drilled. Grease guns should be used to fill the port in the chuck end once a shift; a medium (No. 3) grease is well adapted to this purpose. Hard grease must not be put into the lubricators, as it will not flow through that part. Contrary to the popular belief, oiling a machine once or twice a shift does not provide sufficient lubrication; the drills should be oiled once for every 12 or 14 ft. of hole drilled. The rotating handle of a stoping drill is an oil reservoir and is provided with a port for oiling. The rotating handle is packed with wick-ing, or similar material, which causes the oil to feed slowly from the handle to the other parts of the machine. Stoping drills require oil at least twice a shift; lighter oils than castor, such as Arctic Ammonia, may be used. Drills used in shaft sinking can be oiled satisfactorily by placing a good-sized, drop, sight lubricator on the station above the sinking operations and connecting it with the air-line supplying the sinking drills. If this lubricator is properly filled and adjusted, a uniform oiling of the sinking machines will be effected without the necessity of oiling the drills individually. The grease end should be filled at the station or surface before each drilling period. The shift boss should see that the machines are greased and also that the lubricators at the station function properly. The life of the air-drill hose is somewhat shortened by this method, as oil attacks the inner tube; but as some oil is always present in the compressed air, this is not a serious objection to the method.

Jan 1, 1922

CHARLES F. WILLIS,* Bisbee, Ariz. (written discussion ?).-There are few mine officials who will not say that there is, great need of vocational schools in mining communities, but the absence of success of so many of these ventures makes them wary about establishing such schools. They have neither the time nor the facilities to study the systems and to analyze the factors that have made certain schools a success and others a failure. In the first place, it is difficult to secure the proper instructors. Educators cannot make the appeal to the workmen, because of their lack of experience, and experienced men who are capable of the appeal are not usually educators, knowing nothing about the presentation of the subject. Then, too, there is ordinarily no objective in a mine school. The workman is not reached by a school that makes him merely a more valuable man to his employer, unless he can participate in the gain. An objective, as promotion or financial gain, would appeal to the man and would make for regular attendance. Usually vocational schools are run like all others-a number of subjects at a time, continued from one day to another. This is impractical for the workman, whose mind cannot work like the mind of a school boy. The school boy is spending most of his time in school work, while the man is doing it as a side issue, and he cannot be expected to pick up tonight's lesson where last night's left off. The workman is accustomed to the idea of completing a job and doing one thing at a time; his mind is trained that way, and for this reason a school that works on the principal that each lesson is a complete job, with no reference to the previous or following lesson, will go a long way toward removing one of the things that has caused many failures. The usual vocational schools .in mining communities are either very elementary, or are run by the engineering staff and, consequently, are too advanced. There is no plan between. It is believed that there is a possibility of a halfway type, but this is a subject that is large enough for a paper by itself and is entirely, too broad to be presented as a discussion.

Jan 6, 1919

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947

By M. E. Lombardi

THE Coalinga oil field is located on the west side of the San Joaquin Valley, California. The structure is in general a monocline, the edges of the oil horizon resting on the foot hills and dipping gently toward the east. One prominent anticline occurs plunging southeast. The earlier drilling was done in the foot hills comparatively near the outcrop and the wells were shallow. The sands were followed eastward and, in the case of the anticline, along the plunge, the wells becoming deeper and deeper until the depth of 4,000 ft. was reached and passed. There is nothing to show that the oil will not be found in quantity at still greater depth. In fact, some of the best producers have tapped the sand at close to 4,000 ft. The recovery of oil still farther to the east, and therefore at greater depth, seems to be mainly a question of drilling. In this territory the formations drilled through are chiefly sands and shales; they will not "stand up" in an open drilling hole; the casing has to be carried close to the bit, and it is always difficult to keep the casing free for any considerable distance. Ability to carry casing of comparatively large diameter without conductor pipes for distances of 2,000 or 3,000 ft. or over is desirable in such territory chiefly for two reasons. It makes it possible to enter the oil sand with a pipe of ample diameter; it eliminates one or more expensive strings of casing which act only as conductors for the water string, and furthermore, in territory where waters are encountered which corrode steel rapidly, it makes possible the construction of a rust- and alkali-resisting water string. It is always desirable to shut off top waters, which may lie within 100 ft. or less of the oil sand, with 10-in. pipe. Where the depth is so great that a practical weight of 10-in. pipe will not withstand the probable collapsing pressures, 8 ¼ in. at least is desirable. About the limit of rotary drilling to date in California seems to be the setting of the 10-in. string at 3,200 ft., although the rapid advance in rotary work during the past year seems to indicate that this depth may soon be increased. It is my purpose now, however, to treat only of cable-tool drilling.

Jan 2, 1915

By Walter Kauzman

ALL viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.[t] Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem -i.e., the dependence of shear rates on temperature, stress, etc.-from the standpoint of recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of applications.1 RESOLUTION OF MACROSCOPIC SHEAR INTO MICROSCOPIC MOVEMENTS; RESEMBLANCE TO CHEMICAL REACTIONS Just as any large body is made up of many small units, or atoms, so macroscopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for nonturbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove. In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker,4 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the

Jan 1, 1941

By A. U. Seybolt

Since the time this topic was originally treated in 1954, more recent French3,1 work has been published making it advisable to repeat the earlier oxygen solubility experiments, but using iron of a higher purity. Upon repeating oxygen saturation experiments with zone-refined iron, it was found that the oxygen solid solubility was at least an order of magnitude less than previously observed. SINCE the publication of an earlier paper1 (1954) on this subject by the present author, several contributions on this topic have appeared. Meijering2 in 1955 attempted to reconcile recent conflicting solubility data, without reaching any definite conclusion. sifferlen3 (1955) found that iron of high purity appeared to absorb a quantity of oxygen (0.005 to 0.025 pct) approximately proportional to the structural imperfections present, such as polygonization and grain boundary area. However, he also indicated that purity itself was a significant factor. He concluded that very pure iron nearly free of lattice imperfections would have essentially zero oxygen solubility. His second paper4 (1957) supported this contention since a zone-melted iron containing initially 0.0007 pct O analyzed only 0.0006 pct 0 after prolonged soaking at 850°C with an FeO layer on the surface. Because of the discrepancy between the results of Ref. 1 and those of Sifferlen, it seemed desirable to attempt to resolve this disagreement. EXPERIMENTAL PROCEDURE AND MATERIALS The experimental method used by sifferlen3,1 was essentially the same as that of Ref. 1. In this technique thin iron strip with a surface layer of FeO is soaked for prolonged periods at an elevated temperature in order to saturate the iron with oxygen. After two days at temperatures near 800° to 900° C, one would expect that the iron would be in equilibrium with the surface FeO. In the work reported in Ref. 1 there was evidence that two days holding at 8000to 900°C was more than sufficiently long for saturation. Sifferlen used 48 hr at 850°C. Because of the evidence presented by Sifferlen that the apparent oxygen solubility is a function of iron purity, three grades of iron were used as indicated in Table 1. The Bureau of Standards wire was used only for resistivity tests, while the other two irons were used for saturation-analysis tests of the type described above.

Jan 1, 1960

By P. W. Rainier

The Chivor emerald field is situated on the eastern slope of the Andes in the Department of Boyach, at an elevation of about 8000 ft. above sea level. It overlooks the Llanos (plains) of the Orinoco and is watered by many streams flowing into the Rio Meta, the Orinoco's largest tributary. The Rio Meta is navigable from the Orinoco to a point within about 50 miles of the Chivor district and may eventually prove to be the reasonable outlet for the future development of this part of the country. The topography of the district is extremely rugged and mountainous (Fig. I), the difference in elevation between two points on a mining claim 1 km. square being sometimes as much as 4000 ft. The ground is covered with dense forest growth and the available timber is suitable and sufficient for mining purposes, but it is becoming gradually depleted by Indian clearings as the country around the mines becomes settled. The many streams combined with the rough topography give good possibilities for hydroelectric power. The center of population nearest to Chivor is Bogoth, the capital of the republic and a city of some 300,000 inhabitants; the distance is two and one-half days' travel. The first stage of the journey from BogotB is accomplished by rail to Choconta, some 4 hr. travel. From Choconth the journey is made in the saddle, one night being spent in Guateque. The latter is a small town and the nearest post office to the mines, being some 10 hr. ride distant. The roads are mere bridle paths, in parts hazardous and almost impassable in the wet season. All supplies brought to the mines, other than those produced locally, are carried by pack mule; mule freight from Choconth costs 3 centavos1 per pound. The climate of the Chivor district is healthful and bracing. The wet season begins in March and concludes in November, the remaining months being dry. The annual precipitation is about 130 in. The temperature throughout the year is nearly constant, varying from about 45" F. to about 65" F. shade temperature. The rains are cold and unpleasant, and for the greater part of each day in the wet season the country is shrouded in dense mist. A fire can with comfort be kept burning in a living room all the year round. There are a few slight

Jan 1, 1931

By P. W. Rainier

THE Chivor emerald field is situated on the eastern slope of the Andes in the Department of Boyacá, at an elevation of about 8000 ft. above sea level. It overlooks the Llanos (plains) of the Orinoco and is watered by many streams flowing into the Rio Meta, the Orinoco's largest tributary. The Rio Meta is navigable from the Orinoco to a point within about 50 miles of the Chivor district and may eventually prove to be the reasonable outlet for the future development of this part of the country. The topography of the district is extremely rugged and mountainous (Fig. 1), the difference in elevation between two points on a mining claim 1 km. square being sometimes as much as 4000 ft. The ground is covered with dense forest growth and the available timber is suitable and sufficient for mining purposes, but it is becoming gradually depleted by Indian clearings as the country around the mines becomes settled. The many streams combined with the rough topography give good possi-bilities for hydroelectric power. The center of population nearest to Chivor is Bogota, the capital of the republic and a city of some 300,000 inhabitants; the distance is two and one-half days' travel. The first stage of the journey from Bogota, is accomplished by rail to Chocontá, some 4 hr. travel. From Chocontá the journey is made in the saddle, one night being spent in Guateque. The latter is a small town and the nearest post office to the mines, being some 10 hr. ride distant. The roads are mere bridle paths, in parts hazardous and almost impassable in the wet season. All supplies brought to the mines, other than those produced locally, are carried by pack mule; mule freight from Chocontá costs 3 centavos1 per pound. The climate of the Chivor district is healthful and bracing. The wet season begins in March and concludes in November, the remaining months being dry. The annual precipitation is about 150 in. The temperature throughout the year is nearly constant, varying from about 45° F. to about 65° F. shade temperature. The rains are cold and unpleasant, and for the greater part of each day in the wet season the country is shrouded in dense mist. A fire can with comfort be kept burning in a living room all the year round. There are a few slight

Jan 1, 1929

By R. G. Grieves, G. Thodos

A method is presented for the accurate calculation of the cricondentherm and cricondenbar pressures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain six and quite possibly any number of components including paraffins, isoparaffins, olefins, acetylenes, naphthenes and aromatics. The approach is similur to that used for calculating critical pressures and cricondentherm and cricondenbar temperatures. The critical pressure, the normal boiling point and the approximate vapor pressure behavior of each component are all that art required. A stepwise culculation procedure is necessary for mixtures containing more than two components. From an analysis of 22 binary systems and 118 mixtures, the average deviation of calculated cricondentherm pressures from reported values is 2.4 per cent. For nine multicomponent mixtures the average deviation is 1 per cent. Considering 19 binary systems and 108 mixtures, the average deviation of calculated cricondenbar pressures from reported values is 1.7 per cent. For 15 multi-component mixtures, the average deviation is 2.2 per cent. INTRODUCTION A knowledge of the phase behavior in the critical region of multicomponent hydrocarbon mixtures is of value both in industrial processing operations and for the optimum operation of gas condensate reservoirs. Accurate methods of calculating the critical temperatures and critical pressures4,6,7,8,9,23 and cricondentherm and cricondenbar temperatures6p10 of multicomponent hydrocarbon mixtures are available in the literature. If the cricondentherm and cricondenbar pressures could be calculated with equal accuracy, the entire phase diagram of a multicomponent hydrocarbon mixture could be well approximated. The work of Etter and Kay6 is limited to systems containing the normal paraffins and has not been tested on systems containing a heavier component than heptane. In addition, the development of their multicomponent equations is based upon a limited number of mixtures containing from three to six components. Silverman and Thodos have considered systems containing both paraffinic and non-paraffinic hydrocarbons, but their correlation is limited to binary systems and is highly inaccurate for methane systems. Eilerts has done extensive work on the cricondenbar pressure; he has produced an excellent correlation for binary systems. However, his procedure for multicomponent mixtures is chiefly useful for highly complex mixtures requiring a knowledge of the vapor-liquid equilibrium behavior of the mixtures; he has not considered the cricondentherm pressure. The objective of this study was the development of an accurate and rapid method for the calculation of the cricondentherm and cricondenbar pressures of multicomponent mixtures containing all types of hydrocarbons and having a wide volatility range. The approach that was adopted is similar to that used by Grieves and Thodos for cricondentherm and cricondenbar temperaturesl0 and for critical pressures.9 However, methane systems had to be considered separately and a modified stepwise calculation procedure was utilized for the cricondertherm pressure. The correlations were developed in a manner similar to those for critical pressures and cricondentherm and cricondenbar temperatures. Based upon binary data reported in the literature it was observed that the ratios of cricondentherm and cricondenbar pressure to the pseudocritical pressure (molar average), pt/ppc and pp/ppc, respectively, in two-component systems depended upon the mole fraction of the low-boiling component and upon the diversity in properties of the two components. A dimensionless boiling-point parameter Tb,/Tb was chosen to represent the diversity in properties of the components. For a binary system, Ti,'is the molar average of the normal boiling points of the two components involved. For a multicomponent system it is either the molar average of the normal boiling points of all of the components involved or the molar average of the normal boiling point of the pure low-boiling component and of the atmospheric boiling point of the low-boiling-free mixture of

Jan 1, 1965

By E. T. Turkdogan, P. Grieveson

Experimental results are presented for the rate of solution of nitrogen in a iron in the temperature range 750° to 873°C and in 6 iron in the temperature range 1410° to 1470°C. It is shown that the rate controlling process is diffusion of nitrogen into the iron. The diffusiting of nitrogen in a and 6 iron is derived from the results, and the temperature dependence of the diffusivity is represented by the equation D = 7.8 x e- 18,900/RT sq cm per sec. The solubility of nitrogen in a and 6 iron, in equilibrium with 1 atm pressure of nitrogen, has been measured. Using these results and other available data, it is found that the variation of the logarithm of nitrogen solubility with the reciprocal of absolute temperature is nonlinear. In an Appendix, some results of Darken and Smith are presented for the rate of solution of nitrogen in iron using ammonia + hyidrogen mixtures. These data also support the view that diffudsion of nitrogen in iron is the rate-controlling process when ammonia + hydrogen mixtures are used. A considerable effort has been made to obtain data on the solubility1-5 and diffusivity of nitrogen in a iron6-l2 because an understanding of the effect of nitrogen on the properties of steel must be based on an accurate knowledge of the properties of nitrogen in pure iron. However, no information is available concerning the kinetics of solution of nitrogen in a and 6 iron. Recently the authors13 have investigated the rate-controlling mechanism operating in the kinetics of solution of nitrogen in y iron. This study was directed to determine the rate-controlling processes for similar reactions with a and 6 iron as well as to establish values for the solubility of nitrogen in equilibrium with nitrogen gas in a and a iron. EXPERIMENTAL The procedure used in experiments to determine the rate of solution in cylindrical iron rods was the same as that described in a previous communication.13 Ferrovac E grade iron used in all experiments contained the following impurities in weight percent: C, 0.005; Mn, 0.001; P, 0.002; S, 0.006; Si, 0.006; Ni, 0.025; Cr, 0.002; V, 0.004; W, 0.02; Mo, 0.01; Cu, 0.001; Co, 0.01; 0, 0.007. After cleaning the surface, the iron rods were treated in an atmosphere of purified hydrogen for 17 hr before the reacting gas was introduced for known experimental times. After quenching, the samples were sectioned radially and analyzed for nitrogen. In addition to experiments using rods, iron foils were used in the measurements of solution rates of nitrogen in a iron. The foils of two different thicknesses were prepared by cold rolling Ferrovac E grade iron cylindrical rod to 0.051 and 0.152 cm. Foil samples were used in a rectangular form 5 cm long and 1.25 cm wide. The specimens were thoroughly cleaned of surface oxide with fine emery cloth and degreased with carbon tetrachloride immediately before entry into the furnace. The experimental procedure was the same as that used in the study with rods. At the completion of an experiment, the foil samples of the nitrogenized iron were analyzed for nitrogen after discarding 0.3 cm from the perimeter of the specimen. Iron foils were nitrogenized and denitrogenized in the a and 6 range with a gas mixture of 95 pct N and 5 pct H for times varying from 5 min to 2 hr. Results obtained for the average composition of nitrogen in iron for these experiments are presented in Fig. 1. Prior to the denitrogenization experiments, the samples were saturated with nitrogen at 1000°C and 0.67 atm N, giving a uniform nitrogen concentration of 0.0204 pct. According to the known a-y phase boundary in the Fe-N system,14 this composition lies within the ferrite region at temperatures 750" to 850°C. Use of this initial nitrogen content insured that reaction occurred between the gas and a single solid phase, a iron. Examples of the results for the mean concentrations of nitrogen in cylindrical iron rods, 0.356 cm radius for both the a and 6 ranges are given in Fig. 2. Typical examples of the results obtained for the radial distributions of nitrogen in rods are presented in Fig. 3. It appears that the results for radial distributions can be extrapolated to constant surface compositions which agree with the equi-

Jan 1, 1964

By Leonard B. Lipson

Boyer, Morgan and Muskat,' with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,' have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/'E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951

By Leonard B. Lipson

Boyer, Morgan and Muskat,' with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,' have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/'E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951

By V. Patarini, M. Salkind

BECAUSE of its high strength and stiffness coupled with low density, continuous boron filament is showing great promise as a potential reinforcement for both metals and nonmetals. Of primary consideration for structural applications is the fatigue behavior of boron fiber composites. Composite fatigue behavior is dependent upon three factors: 1) fiber fatigue behavior, 2) matrix fatigue behavior, and 3) the effect of the interface and fiber ends. The purpose of this note is to describe the behavior of boron filament in rotating beam fatigue. The filament, described by Talley' and Galasso, Salkind, Kuehl, and Patarini,' was made by the hydrogen reduction of boron trichloride on a hot tungsten filament. Testing was performed using a commercial rotating beam wire fatigue tester* described by Votta.~ One end of the test sample is held in a chuck in a synchronous motor. The sample is bent around in a "U" shape, and the other end inserted into a carbide bushing. The maximum strain occurs at the bottom of the "U" where the radius of curvature is a minimum. The strain is adjusted by adjusting the length of the specimen and the location of the bushing. Samples were rotated at 3600 rpm and an automatic shutoff device used to determine the number of cycles to failure. The measurements were accurate to the nearest 360 cycles. The fatigue behavior is summarized in Fig. 1 for fifty-one samples of 4.8 x 10"3 in. diam fibers and ten samples of 3.2 X 10"3 in. diam fiber. The two sample groups represent two different filament production runs and two different nominal size groups. Both groups exhibited nominal tensile strengths of 400,000 psi. No significant difference in the fatigue behavior of the two sample groups is apparent. The scatter in the data is not unexpected for a brittle filament which exhibits a tensile strength distribution with a standard deviation of 10 to 15 pct. Because the test procedure provides a known outer fiber strain in the sample, the maximum stress was calculated assuming a Young's modulus of 58 x 10' psi. This value was selected as being representative of several nominal fiber sizes.2 All of the samples which failed exhibited sudden, catastrophic fracture, and no permanent deformation. One sample was stopped after 1.66 x lo8 cycles at *200,000 psi. The fiber exhibited no apparent damage or deformation. It is apparent that the fatigue resistance of boron filament is quite good. It can therefore be speculated that the fatigue behavior of boron fiber composites would be controlled by the "weaker links", namely matrix fatigue resistance and interface behavior. In fact, preliminary investigations have revealed that this is true for boron-reinforced aluminum? It should be noted that the data presented herein may not necessarily reflect the tensile fatigue behavior of boron filament. It is well-known that boron filament has a radial residual stress pattern with the outer surface in ~om~ression.~ Because of this fact, tensile failure is normally nucleated in the interior of the filament.5 Since the data presented herein is for a rotating beam test in which only the outer surface of the fiber is stressed to the maximum value, it would be incorrect to assume that the failure mechanism and fatigue behavior would be the same if the fiber were tested in tensile fatigue. The fact that many of the data are well above the nominal 400,000 psi tensile strength would tend to support this argument. The authors would like to express their appreciation to the United Aircraft Research Laboratories for supporting this investigation and for permission to publish the results. A portion of this effort was supported by the Air Force Materials Laboratory under contract AF33(615)-2125.

Jan 1, 1968

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953