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By C. R. Dodson, D. Goodwill, E. H. Mayer

The paper summarizes the historical background of the pressure-volume-temperature analyses of reservoir fluids, the errors involved in both the sampling and testing of reservoir fluids, the type of information required of a PVT determination, and the field conditions that limit the application of any one analysis. Particular emphasis is placed on the necessity for approximating as closely as possible the liberation sequence occurring in the producing formation, flow string, and surface separators. A combined differential and flash or "composite" liberation is suggested as the best means of approximating this liberation sequence. HISTORICAL BACKGROUND Petroleum reservoir engineering commonly is considered to be one of the newest fields of petroleum science, yet much work of a theoretical and intuitive nature was done many years before the modern techniques of reservoir analyses were developed. The period 1910-1924 saw considerable work in the field of reservoir behavior done by the U. S. Bureau of Mines. This work:.' although entirely theoretical, pointed out the importance of gas in the recovery of oil from the reservoir. The statement by J. 0. Lewis that 20 per cent or less of the oil originally in place in a pool was recovered from the ground under uncurtailed production conditions caused some operators to re-examine and modify their production methods. However, though these works showed methods of production that have subsequently resulted in greater oil recoveries, they in general went unnoticed, even though there was a fear that the nation's petroleum resources were being exhausted. The period 1924-1933 saw the industry take considerably more interest in reservoir behavior because of an unfounded fear of its inability to replace oil reserves, the possibility of government regulation, and the energy of one man, Henry L. Doherty. Doherty aroused heated discussions in the industry concerning conservation. To prove or disprove his theories the first experimental work on the reservoir behavior of petroleum was undertaken. The papers of Dow and Calkin,' Beecher and Parkhurst," and Mills and Heitheckere are classics although their experimental procedures were crude. These papers proved that the properties of petroleum in the reservoir are quite dissimilar to the properties measured at the well head. Gas dissolved in the oil phase was recognized as having considerable importance as had been predicted by the earlier theorists. Slightly later Miller and his co-workers assembled the first text correlating all the known data on the reservoir behavior of petroleum and used, these data to show the economic value of conservation. Quantitative application of pressure-volume-temperature analyses of reservoir fluids was given in the paper of Coleman, Wilde, and Moore"; this work showed that with sufficient laboratory and production data prediction of reservoir behavior was possible. The refined sampling and labora-

Jan 1, 1953

By F. L. Fayers, J. W. Sheldon

It has been a matter of concern to the petroleum industry to determine what effect the capillary term has on saturation profiles, since these profiles determine ultimate economic oil recovery. In their original solution of the non-capillary two-phase flow problem, Buckley and Leverett&apos; showed that solutions of the two-phase flow equations became multiple-valued in saturation. Since it is physically unrealistic for saturation to have more than one value at a given position, Buckley and Leverett resolved this difficulty by introducing a saturation discontinuity or "shock". They evaluated the strength and position of the shock from material balance considerations. Recently Sheldon, Zondek and Cardwell&apos; have demonstrated that the method of characteristics can be used to solve this and related problems. Owing to capillarity it is physically unlikely that saturation shocks occur in an oil reservoir. Buckley and Leverett suggested that the effects of interfacial tensions should be included in the fluid flow equations, if the solutions are to give continuous single-valued saturation distributions. An analogy to this problem is encountered in the theory of wpersonic compressible flow where the introduction of the viscous term eliminates shock behavior. However, the mathematical form of the capillary term in the porous medium fluid flow equations differs from the viscosity term in the Navier-Stokes equation. This paper demons~rates that capillarity does eliminate the triple-valued behavior and indicates the magnitude of capillary and gravity effects on the saturation profile for a variety of systems. DERIVATION OF LAGRANGIAN AND EULERIAN FORMS OF THE DISPLACEMENT EQUATION The equations representing capillary, two-phase flow are given by applying Darcy&apos;s law and a material balance condition for each phase. The familiar Darcy and material balance equations are as follows. ^U*^0......<3, ^^r=°......c« S is the saturation of the water phase, and B the inclination of the porous medium. Pressures in the oil and water phases differ by the capillary pressure associated with the interfacial tensions, P.-P.=pAS)..........(5) where p, is determined experimentally. The porous medium is said to be oil-wet if P, > Po and water-wet if P, < Po. If the fluids are incompressible and the total volumetric flow rate, q, is constant, then v, f v,, = q...........(6) By eliminating P.. /»,, and v, from Eqs. 1, 2, 5 and 6 it follows that It is convenient to normalize the variables in the problem after the manner of Handy and Hadley% so that Eqs. 3 and 7 become where j,, = —, the fractional flow of water; (F, is a capillary pressure normalizing constant.) Substitution of Eq. 9 into Eq. 8 gives In this partial differential equation for an initial value

By H. Le Chatelier

An evident connection exists between chemical and calorific phenomena: the most important, of our sources of heat, the combustion of coal, is nothing else than a chemical reaction. Not satisfied with this indefinite statement, investigators have attempted to establish a more precise correlation between these two orders of phenomena, and have questioned whether there be not a necessary connection between the possibility of a chemical reaction and the algebraic sign of the quantity of heat which it would call into play (i.e., liberate or absorb). This question possesses the highest interest for metallurgical chemists. But the study of it by experimental methods only could not completely elucidate it. To arrive at a definite solution, it was necessary to appeal to a science much more general than chemistry,—namely, that of energetics, which embraces all the physical sciences. We can place absolute confidence in its conclusions, because they rest upon a proposition which can scarcely be denied, namely, the impossibility of The main facts in the history of the development o‡ this field of Triassic coals have been already set before the Institute in the papers of Mr. Oswald J. Heinrich, a former member of the Institute and the superintendent of the mines at Midlothian. † From these and other references to the field, it appears that coal was known to exist here as early as 1701; for on the 10th of May that year Colonel Byrd reported to the Colonial Council of Virginia the discovery of coal. Coal was mined from 1770 to 1780; but the amount shipped is unknown. It was much used in Richmond at this early date for gratefires. In 1789 shipments were made to northern ports. During the first half of the century just passed, mining operations attained in this field their greatest development, the number and extent of the collieries and the tonnage of coal raised per annum being greater for that period than for any similar period since. The maximum annual output exceeded 100,000 tons, while in two years only since the Civil War has the amount of coal raised exceeded 50,000 tons. This field covers about 150 sq. in. Its outline and the position of the strata in which the coal-outcrops occur are shown on the accompanying map, reproduced from the latest survey by the U. S. Geological Survey. Mining has been carried on along the margins of the area, often in the primitive manner in vogue at the beginning of operations, by means of shafts and slopes, usually too small in cross-section to permit the proper working of the beds. Most of the output has been won from

Jan 1, 1902

By Edward C. J. Urban

The nature of certain pernicious dusts commonly encountered in the removal of iron ore from the underground mines of the Lake Superior district is recognized, and appropriate measures for the protection of individuals subjected to these dusts have been applied in most mines for more than 10 years. Undoubtedly the principal concern has been demanded by dusts that contain as a constituent silicon dioxide in its free or uncombined state, the mineral we all know as quartz or chert. Investigators1 agree that among the factors that determine injurious exposure are: the composition of the dust, the concentration suspended at the breathing level and the duration of the exposure. We have on hand data that describe the experience of several underground iron-ore mines in the Upper Peninsula of Michigan and Wisconsin in regard to these factors, which in a large measure also reflect the general experience of the other mines of the area. We believe that a discussion of these data will indicate the effectiveness of the dust-control methods that have been considered good practice and that have been employed over a long period of time. A silicosis-prevention program was ini- tiated by the iron mines of the Upper Peninsula in 1934 and records of mine dustiness are available from that date to the present time. For dust conditions previous to 1934 the results of observations conducted in other industries can be utilized together with local information pertaining to the development and initial application of rock-drilling equipment. Development of Rock DriI,I.s Thc earliest percussion rock drill that later had any industrial use was patented in this country in 1851.2 This machine was later modified and improved in many respects but its Piston-Type design remained standard for drilling equipment in most mines for the next 63 years.3 The piston drill was operated either by air or by steam. It employed a solid drill steel, fastened directly to the reciprocating piston. The drilling was done dry except in holes directed at an angle below the horizontal. For these water was manually injected into the hole and the pumping action of the rod expelled the sludge. The dry cuttings from drillings inclined above the horizontal fell from the hole by their own weight. A development of major importance from the standpoint of dust generation and control occurred with the invention by J. G. Leyner of a hammer-type rock drill that embodied the essential feature of a drill steel with a hollow core. His patent was secured in 1897. The machine was a radical departure in drilling method. The steel was held loosely in a chuck while

Jan 1, 1949

Discussion of the paper of WALTHER MATHESIUS, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 539 to 555. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-This paper answers. partly the difficult questions which have come up as to why it is not economical to use higher blast temperatures in the smelting of Mesaba ores, such as the high temperatures used in European practices, and the answer is very plain that the ores will not stand the higher temperature. But the paper does not go into detail as to what special difficulties were found with the higher temperature of blast, and I would ask the author to kindly specify them. W. A. FORBES, New York, N. Y.-A large part of the troubles that furnace men experienced in using high-blast heats in smelting Mesaba ores in the early days of using Mesaba ores, was clue to the attempt to use these soft ores on furnaces having the same lines as the furnaces used in smelting the hard Old Range ores. As the result of observation and study, the dimensions of the lower part of the blast furnaces have been changed and the difficulties of the blast-furnace men in operating with a large percentage of Mesaba ore and high-blast temperatures have been largely overcome. The changes I refer to in particular are: (1) steepening the angle of the bosh; (2), decreasing the height of the bosh; (3) increasing the diameter of the hearth. JOSEPH W. RICHARDS.-Mr. Forbes&apos;s answer is quite satisfactory, and the moral which it points is that when the furnace is run with a higher temperature in the smelting zone, the furnace lines which were adapted for the lower temperatures are not necessarily those best suited for the higher hearth temperatures. If. enriched blast were used in a furnace, and higher temperatures run, it would be found necessary to further modify the lines of the furnace to meet the new conditions and to get the maximum output with economy. J. E. JOHNSON, JR., New York, N. Y.-It seems to me this is one of the few papers which could well have been a little longer. The data which Mr. Mathesius has given us, I think should be considered in connection with the paper which Mr. Brassert read before the American Iron and Steel Institute last spring, in which he described how they had obtained remarkable results with furnaces with steep but very short boshes; the angles have been raised to 80°, and the boshes made so short that they no longer appear as a conspicuous part of the shape of the furnace.

Jan 5, 1915

By Joseph J. Yancik, Leonard L. Felts, George B. Clark

LITTLE information has been published concerning the actual or useful amount of energy obtained from explosives when they are used for blasting. To provide more data on this subject, 8-in. neet cement cubes were blasted in a steel plate box and the breakage energy evaluated by comparison with drop crusher results using Rittinger&apos;s,1,2 Kick&apos;s: and Bond&apos;s&apos; theories. Theories by Bond and Wang," Lineau," Hatch,&apos; Roller,&apos; and others0-11 were not considered applicable. Those used in this investigation may be expressed mathematically as follows: Rittinger Theory E = KrS2, pet,—--------------- [1] 40 d1 d0 Kick Theory TV 1 1 E = =K, [S pct. log1/d+ 100 log d0] [2] 40 d1 L. L. FELTS, Junior Member AIME, was formerly a Graduate Assistant, University of Illinois. G. B. CLARK, Member AIME, was formerly Professor of Mining Engineering, University of Illinois, and is now Chairman, Dept. of Mining Engineering, Missouri School of Mines and Metallurgy. J. YANCIK, Junior Member AIME, is a Graduate Assistant, Missouri School of Mines and Metallurgy. This paper, TP 4213A. is revised from a thesis submitted by L. L. Felts in partial fulfillment of the M.S. degree in Mining Engineering, University of Illinois, 1954. Discussion may be sent (2 copies) to AIME before May 31, 1956. Manuscript, Dec. 27, 1954. Bond&apos;s Third Theory E = Kb [S pct. log1/d1+ 100 log d0] where E — energy used in breakage, d, = average diameters of screen fractions of broken cement particles, pct, = percent weight of diameter d;, and 2 pct, = 100 pct. The above equations were employed to determine values of Kr, Kk, Kb for particle size distributions similar to those obtained from the blasting curves. These values were in turn used as a means of approximating the specific energy of the blasted material. The efficiency of crushing by blasting was then determined by dividing this specific energy by the maximum available work of the explosive per gram of cement. Knowledge of the failure of solids under static loads is developing very rapidly. Their failure under impact loads has been investigated and reported in the literature only to a limited extent. Theories of failure&apos; hnder static loading include 1) the maximum stress theory, 2) the maximum strain theory, 3) the theory of constant elastic strain, 4) theory of maximum shearing stress, and 5) Mohr&apos;s theory of strength. All of these have elements of usefulness in establishing an applicable theory for blasting. For highly strained and compressed material such as that surrounding a detonating charge of high explosive, the Mohr theory and its implications appear to be the

Jan 1, 1957

C. P. BOWIE, San Francisco, Cal.-In my work with the U.S. Bureau of Mines, I have been detailed to report on oil storage containers, and in going around the country I have, been much interested in, the possibilities in the use of concrete for such containers. In talking with a good many people, I have discovered that concrete is being used A good deal for a wide variety of oils ranging from 14° to as high as 40° Bé., especially, by some of the western railroads:, If any member has had experience, in storing gasoline in concrete, I should like to learn of it. DORSEY HAGER, Tulsa, Okla.-Mr. M J. Munn, formerly .with the U. S. Geological Survey, acid connected with the Gypsy Oil Co., until a short time ago, has invented a invented a method for the application of concrete to the storage not only of crude oil but of refined products:. The Cosden Oil Co., of Tulsa, is now working on that plan, and, expects to store refined products in concrete tanks. THE CHAIRMAN (I.N. KNAPP, Ardmore Pa.).-I have had considerable experience in building masonry tanks for gas Holders. I do not believe it is possible to build a concrete or masonry tank of any kind. With hydraulic cement, mortar, which will be absolutely water-tight, unless the bottom and inner wall, after completion are waterproofed with some impervious material. The same will be true of oil tanks, the bottom and inner face of which must be made impervious to oil. Masonry tanks are intended to be sunk in the ground. All that the wall of the tank then amounts to is a retaining wall to keep the excavation in shape and to receive an impervious coating. The bottom of, a; tank, when empty, must be protected by a relief valve from any hydraulic: pressure acting from below. At ordinary prices, for sheets, a tank 100 ft. diam by 20 ft. deep can be built of steel much quicker and cheaper than of masonry. Several years, ago I saw very large oil storage tank under construction in California the bottom and sides being concrete. The sides were, sloped at about the single of repose for the material excavated: If you build a steel oil tank, you can get. .men for the work who do nothing else, and you, are likely to get a satisfactory job; but if you wish to build a concrete or masonry tank it is almost: impossible to find men skilled in building absolutely water-tight masonry Work. The general idea is that any laborer can mix up concrete in any old way and make a,

Jan 1, 1918

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government&apos;s hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government&apos;s hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By G. Aertsen

THE CHAIRMAN (HENRY D. HIBBARD, Plainfield, N. J).-This excellent paper fills a gap in our Transactions and is most acceptable. In the early days another way of casting tire ingots, sometimes called cheeses, because of their shape, was to use a 22-gage sheet-iron cylindrical can for each ingot of the proper size to give the weight desired. These cans were bottom cast in groups, usually of four, each can being surrounded by a heavy iron ring somewhat taller than itself the top of the can being covered by a circular cast-iron plate having a small conical riser in the center, about 2 ½ in. in diameter at the bottom and 10 in. high. The top plate was clamped down to resist the upward pressure of the fluid metal and the space between the can and the outer ring, usually about 2 in. wide, was filled with dry sand. The riser permitted the escape of some of the air displaced by the steel and also increased the pressure in the steel when the mold was filled, and so diminished somewhat the tendency for gas holes to form. But little was known of segregation and pipe in those days, though the center of an ingot was understood to be the worst part, and it was separated in part in the disk which was punched out in perforating the ingot. This disk was about 8 in. in diameter and from ¾ to 2 in. thick, the variation in thickness being to rectify the weight. When an ingot was too -heavy, a thicker disk-was made by not driving the punch in quite as far as when the ingot-weight was right. Then the bloom was turned over and the punch driven in on the other side, which finished the punching and detached the disk. The tire bloom was then" becked" and later reheated and rolled as described in the paper. The forging was done with a 10-ton double-acting steam hammer. The steel generally speaking had lower carbon, from 0.45 to 0.55 per cent., than tires today have, and the tires were smaller, the most common size of ingot weighing 1,060 lb. each. BRADLEY STOUGHTON, New York, N. Y.-This paper was specially requested by the Iron and Steel Committee, because that Committee thought so important an industry should have its history written by one who was familiar with it, and before he had forgotten, or all the rest of the world had forgotten, its early stages. Mr. Aertsen has said that it is not an exhaustive research. I think it would not be any different if it were an exhaustive research, because our library made a careful attempt to find some written light on the history of these tires, but very little was found.

Jan 4, 1917

By J. Warner, M. J. Marcinkowski, B. Cullen, T. Prevender, J. Mcllwain, T. Carnahan, J. Pahlman, J. Demel, J. Munford

The following analysis was an outgrowth of a midterm examination given by one of the authors (M.J.M) in a course entitled Metallurgy 541 "Applications of Dislocation Theory&apos;&apos; at Iowa State University. Fig, l(a) shows the three-layer sequence of atoms lying in the (111) plane which characterizes the fully ordered AB3 fcc crystal, i.e., LI2 type. If any two-layer sequence of close-packed planes is constructed from Fig. 16)&apos; the structure would be hcp of the DO,, type. Consider for convenience that the circled atoms lie in the plane of the drawing while those shown square and triangular lie immediately above and below the plane of the drawing, respectively. It has already been shown&apos; that if a Shockley partial dislocation is passed over the plane of the paper, then the square atoms in Fig. 1(a) are displaced from their original positions as shown by the arrows in Fig. l(b). Not only is an intrinsic fault produced but the crystal is simultaneously disordered across the slip plane. In particular, 2AB bonds are converted to 1AA and 1BB bonds when referred to the area outlined by the solid line in Fig. 1. If, on the other hand, a Shockley partial is allowed to pass immediately above and immediately below the plane of the paper so as to displace the atoms in opposite directions as shown in Fig. l(c), an extrinsic fault is producedZ and twice the amount of disorder is introduced into the crystal as compared to the dislocation-produced intrinsic fault, if only broken first-neighbor bonds are counted. If an intrinsic stacking fault is produced by removing a close-packed plane of atoms in Fig. l(a) and displacing the two adjacent planes by 1/3a0[111], no wrong nearest-neighbor bonds are produced. Similarly, if an extra half plane of atoms with the same arrangement as any of those shown in Fig. l(a) is inserted between any two planes in the same figure, then an extrinsic stacking fault is produced in which once again no wrong nearest-neighbor bonds are produced. The latter two faults are bounded by Frank partial dislocations. Since, at least in the alloy CU3AU,3 nearly all of the ordering energy resides in the first nearest-neighbor interactions, intrinsic and extrinsic stacking faults and associated APB&apos;s of the Frank type are expected to have significantly lower energy than those of the Shockley type in CusAu in particular and quite likely in L1, and DO19 type alloys in general. Also, because of the higher degree of disorder plus loop interaction

Jan 1, 1968

A SPRING meeting is to be held at Cleveland this month under the joint auspices of the Iron and Steel Committee and the Ohio Section with the cooperation of the neighboring sections in Pennsyl-vania, Illinois, and the other States of the Great Lakes region. The discussions will be focused on just one subject, that of manganese, but will cover that thor- oughly as is indicated by the following list of papers. TECHNICAL PROGRAM Some Political Aspects of the World Manganese Situa-tion. By C. K. Leith, Professor of Geology, Uni-versity of Wisconsin, Madison, Wis. Manganese Resources in Relation to Domestic Con-sumption. By J. V. W. Reynders, Consulting En-gineer, New York, N. Y. Manganese Deposits of the&apos; Gold Coast, Africa. By Sir Arthur E. Kitson, Director of the Geological Sur-vey of the Gold Coast, London; with Notes on the Petrology of Certain Associated Manganese Silicate-bearing Rocks. By Maj. N. R. Junner. Reserves of Lake Superior Manganiferous Iron Ores. By Carl Zapffe, Manager, iron ore properties, North-ern Pacific Railway Co., Brainerd, Minn. Iron Manganese Alloys Low in Carbon. By. Sir Robert Hadfield, Hadfields, Ltd., London. Manganese in Non-ferrous Alloys. By M. G. Corson, Consulting Engineer, New York, N. Y. Importance of Manganese in the Steel Industry. By H. M. Boylston, Professor of Metallurgy, Case School of Applied Science, Cleveland, Ohio. Minnesota Manganiferous Iron Ore in Relation to the Iron and Steel Industry. By T. L. Joseph, E. P. Barnett and C. E. Wood of the North Central Min-ing, Experiment Station, U. S. Bureau of Mines, Minneapolis, Minn. Representatives of the leading steel companies, the Army, the Navy, the Geological Survey, Bureau of Mines, and leading technical societies will be present and a lively discussion of the various papers is already assured. Nearly 14 pounds of manganese is needed for every ton of steel made. Estimates indicate that the total reserves of ore in this country suitable for making ferro would hardly supply domestic requirements for ten years, even if it could all be mined in that time. The grade of ore called for by present practice must come from abroad. The present tariff policy of this country is stated to cost industry $8,000,000 in order to force production of manganese ore to the extent of $600,000. What is the wise thing to do? Should a stock be accumulated? If so, how? Is it feasible to change practice and use low-grade ore or to beneficiate the ores of this grade and meet our requirements? What progress is being made in this direction? ,These and similar questions are raised in the various papers that have been submitted and will be open for dis-cussion.

Jan 3, 1927

By Grafton M. Thrasher

Discussion of the paper of GRAFTON M. THRASHER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 106, October, 1915, pp. 2129 to 2138. RICHARD MOLDENKE, Watchung, N. J.-Mr. Thrasher is to be commended for developing a very interesting comparison between high- and low-carbon and silicon malleable cast irons for an equal degree of chill. His deductions are unquestionably correct, though the application to daily practice is open to serious criticism, from the standpoint of the man who receives the castings, as will be shown later on. Running over some of the points which affect the tests in question: Mr. Thrasher admits that the temperature of pouring has a serious influence on the degree of chill shown in the test plugs he made. This is a well-known fact, and I would like to add that another serious trouble comes from oxidized iron when the heats have been unduly prolonged. Such metal always shows more chilling action for a given silicon and carbon content than normally melted iron. Indeed, the test piece quoted giving the extreme of the chill line (1.07 per cent. Si and 2.47 per cent. total carbon) was such a poor heat, a ferro-silicon addition never "doctoring" up the metal sufficiently to show normal good strength. In spite of these irregularities, which would simply change the curve slightly, I take it that Mr. Thrasher&apos;s results can be accepted as reliable enough to establish the relationship of silicon and total carbon as shown. When, however, the claim is made that silicon and carbon can be substituted for each other in mixture-making (a claim which may be perfectly correct metallurgically), a very important factor is forgotten, causing the purchaser of the castings much annoyance. This is the contraction (erroneously called shrinkage) of the castings. They will no longer be true to pattern. The lower the total carbon is allowed to drop, the greater the contraction, and increasing the silicon correspondingly will not correct this trouble. No wonder that recently, in revising the Standard Specifications for Malleable Castings it was necessary to increase the variation of castings from requirements considerably over what was formerly found sufficient. The habit of running up the proportion of silicon and escaping danger from grayness of the metal by copious steel additions was evidently too tempting to manufacturers, as their molding losses were thus kept down and a very soft malleable iron resulted. The customer, however, got serious variations in his work, which was not the case when the total carbon was kept between 3.25 and 2.75, and the silicon held as low as possible without undue cracking of the hard castings.

Jan 5, 1916

By Eric Kula, Åke Josefsson

L. J. Dijkstra and R. Sladek, (Ontario Research Foundation, Toronto, and Institute for the Study of Metals, Chicago, respectively)—This interesting paper confirms some results obtained some years ago in collaboration with Fast: namely the broadening of the nitrogen peak by the presence of small amounts of manganese. Later on a more extensive study of this effect was made at the Institute for the Study of Metals at Chicago. As the work has not yet been submitted for publication we wish to mention here briefly some of the results. The effect of about 0.5 atomic pct manganese, chromium, molybdenum, or vanadium on the nitrogen-peak in iron was examined. The broadening found previously in the case of manganese was even found to be more pronounced for chromium. In the case of molybdenum and vanadium a double peak was observed which seemed to justify the idea that in all cases mainly two relaxation times were involved: namely, the normal relaxation time as found in pure iron and a second relaxation time related to the existence of abnormal interstitial lattice sites introduced by the foreign metallic element. The analysis showed that for the normal nitrogen-peak as a reference at 22°C the abnormal peak was found at about 32°, 47°, 75°, and 87°C in the case of manganese, chromium, molybdenum, and vanadium, respestively. In the manganese alloy the free energy difference for a nitrogen-atom at an abnormal and a normal lattice site was estimated at 2800 cal per mol. This means that for temperatures above 100°C the solid solubility and overall diffusion rate of nitrogen is not much affected by additions of 0.5 pct Mn. We believe that the difference in rate of precipitation of nitrogen in pure iron and the manganese alloy is mainly a question of the number of potential nuclei available in the different steels. In studying the effect of these alloying elements on precipitation of nitrogen, a distinction must be made between the para reaction and ortho reaction, using terminology introduced by Hultgren.7 The ortho reaction in which the alloying metallic element participates in the diffusion under formation of nitrides occurs at high temperatures such as 600°C. The para reaction in which the alloying metallic element does not diffuse and in which the nitride inherits its alloy content from the matrix occurs at lower temperatures. To prevent the ortho reaction the alloys have to be quenched rapidly from the phase. It is not surprising that the authors find that the height of the peak indicates a lower nitrogen content than chemical analysis. In the first place the peak is not a single relaxation peak and secondly, the steels were not quenched from the phase after the nitrogen was introduced at 580 °C.

Jan 1, 1953

* A complete magnetic picture of the Mesabi range is now available for the first time with the release of 21 additional maps based on the aeromagnetic survey of 30,000 square miles made jointly by the USGS and the Minnesota Geological Survey. A potential iron formation with a magnetic pattern remarkably like that of the Mesabi iron range lies buried beneath the glacial drift in a wide belt extending some 30 miles across the northwest corner of Itasca County in north central Minnesota. Identification of three new uranium minerals by the USGS was recently announced. The new minerals, andersonite, swartzite, and bayleyite are, respectively, hydrous uranyl carbonates of magnesium, of sodium and calcium, and of calcium and magnesium. They were first observed by Charles A. Anderson, Survey geologist, in a coating on gypsum on the 300-ft level of the Hillside mine, Yavapai County, Arizona. International Minerals and Chemical Corp. has announced a $4,000,000 expansion and development program in the Polk County phosphate fields in Florida, Plants for the manufacture of multiple superphosphate and phosphate chemicals including dicalcium p osphate for animal feed and chemical purposes, and a sulphuric acid are planned. Office building, machine shop, warehouse, and laboratory are also scheduled for erection. A new type of tramp iron detector is being used on the conveyor belt feeder at the South Agnew stripping operation. It is made of an alloy of aluminum, nickel and cobalt and does not have any electric coils. The alloy, known as Alnico, is remarkable for the permanence and intensity of the magnetism which it retains. The detector was made by Dings Magnetic Separator Co. and it is probable that Alnico will be used in magnetic separators. The American Society of Engineering Education estimates that unless the percentage of high school graduates entering engineering colleges is increased, there is a strong possibility that instead of a large surplus of engineering graduates, which has been propehsied rather widely, there will soon be fewer engineering graduates available than are needed annually by our national economy. This conclusion is reached from a survey that shows that engineering enrollments are only slightly higher than prewar whereas industrial expansion is increasing the need for engineers. * The natural resources of Korea are being investigated under ECA sponsorship. E.J. Longyear has just embarked 8 crews for that country; two drills are scheduled for base metal search while six are slated for development of coal reserves. An innovation in the development work in the iron country has been the adoption of the Drill-Mobile, jumbo-mounted drills on rubber-tired carriage, by Cleveland-Cliffs at the Mather A and B mines. The machine is being used to cut stations in the new Mathed B shaft and for driving development headings at the Mather A.

Jan 5, 1950

By L. D. Jaffe, H. C. Mann, E. L. Reed

The authors have recently published1 evidence that brittle transgranular fracture of polycrystalline metals does not originate at a point and propagate continuously across the material, but rather develops at numerous related points, leading to a series of micro-cracks which subsequently link up. Series of related microcracks were observed in steel specimens broken in fatigue—specifically, at the central portions which broke during the final sudden fracture. Microcracks of the type mentioned have also been reported by Baeyertz, Craig and Bumps&apos;2 in steel broken under impact. % Some micrographs published by Irwin3 may possibly be interpreted as showing discontinuous brittle cracks. This paper presents additional observations of the authors on discontinuous crack propagation under various conditions. Impact Test Specimens The impact test specimens were cut longitudinally from a steel forging containing: The heat treatment consisted of oil quenching in a heavy section from 1600°F and tempering at 1260°F. The resulting yield strength was 78,000 psi, tensile strength 100,000 psi, elongation 20.0 pet in 2 in., and reduction of area 55.0 pet. Standard V-notch Charpy specimens were broken in a 217 ft-lb machine at a striking velocity of 16.8 fps. Energy absorption and fracture appearance of this material in the V-notch Charpy test are plotted as functions of temperature in Fig 1. After test, fractured halves of specimens appearing 0, 40, 80, and 100 pet fibrous (to the unaided eye) were electroplated with nickel, sectioned longitudinally (perpendicular to the notch at its midpoint), polished and etched with Cohen-Hurlich-Jacobson (C-H-J) reagent (picric acid plus Zephiran chloride in ethyl ether)4 or with Vilella reagent (1 pet picric plus 5 pct hydrochloric acid in ethyl alcohol).5 Fig 2 and 3 show cracks near the path of final fracture in the specimen rated 0 pct fibrous. Many of the cracks terminate at the boundaries of ferrite grains, some at boundaries of pre- existing austenite gzains. * A crack often starts near the end of another. Cracks within the same ferrite grains are parallel or approximately parallel in several cases. A large percentage of the cracks are branched. Fig 4 illustrated a group of cracks in the 40 pct fibrous specimen. Branching and parallelism are well marked. No more than three directions of crack have been observed on the polished surface in one ferrite grain. This is consistent with the evidence6 that brittle fracture of ferrite takes place on the cube face crystallographic planes: the {100} planes. The appearance of some cracks suggests that they have passed around a projecting corner of a second ferrite grain by going outside the plane of polish. In Fig 5 cracks in the 80 pet fibrous specimen may be observed. Some of

Jan 1, 1950

By P. A. Beck

ACCORDING to a recent hypothesis of Sully,&apos; xY. binary CT phases are characterized by 1.7 bonding 3d electrons per atom, which completely fill the first Brillouin zone. This hypothesis appears to imply that there are no empty 3d orbitals in the u phase, and that, correspondingly, this phase must be dia-magnetic, or at most weakly paramagnetic. On the other hand, Bowen and Hoar&apos; reported that a u phase extracted electrolytically from an alloy steel became ferromagnetic when cooled to about —113°C. In view of the fundamental interest of the problem from the point of view of the electron structure of the u phase, it seemed worthwhile to study the magnetic properties of massive u phase specimens of various known compositions. Sigma specimens of the following compositions were tested: 1—40 atomic pct Fe, 40 atomic pct Cr, and 20 atomic pct Mo 2—35 atomic pct Fe, 35 atomic pct Cr, and 30 atomic pct Mo 3—48.7 atomic pct Fe, 50.2 atomic pct Cr, and 1.1 atomic pct W 4—40.7 atomic pct Co and 59.3 atomic pct Cr All specimens were found to be strongly paramagnetic at room temperature, particularly alloy No. 1. At liquid nitrogen temperature, alloy No. 1 be- came ferromagnetic; the other u alloys remained paramagnetic. Even though apparently not all u alloys become ferromagnetic at liquid nitrogen temperature, in view of their strong paramagnetism it is probable that the electron structure proposed by Sully is not correct. Similar qualitative studies were made with the p, P, and 8 phases." A p phase specimen of 57.2 atomic pct Co and 42.8 atomic pct Mo; a P specimen of 19.9 atomic pct Cr, 37.8 atomic pct Ni, and 42.3 atomic pct Mo; and a 8 specimen of 50.4 atomic pct Ni and 49.6 atomic pct Mo were tested at room temperature, and all were found to be paramagnetic, although considerably weaker than the u phase specimens described above. A test at liquid nitrogen temperature gave similar results for all specimens; none became ferromagnetic. Thanks are due to D. K. Das for preparing several of the alloys and to Pol Duwez of California Institute of Technology for kindly loaning four specimens of cr alloys. References 1 A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, p. 173. - K. W. J. Bowen and T. P. Hoar: Low Temperature Ferromagnetism of Sigma Phase in an Alloy Steel. Research (1950) 3, p. 484. 3 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951).

Jan 1, 1953

By W. Rosotoker

Using an expression for the free energy of a homogeneous phase as a function of composition, a relationship is derived which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. Comparisons between observed and calculated phase boundaries in the systems Fe-Ni, Fe-Mn, Fe-W, Ti-Mo, and Ti-Cb are presented. IT is the purpose of this paper to illustrate how the general free energy equations for two phases in equilibrium may be used to derive an expression which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. The free energy per gram atom of a disordered solid solution may, for many purposes, be represented by the equation:&apos; F = ½NZ [C-V,, + (1-C) VbB + 2C (l-C)V] + K(T) +RT[C-lnC+ (l-C)ln(l-C) ] [1] where N is Avogadro&apos;s number; Z, the coordination number; C, the concentration of the solute element in atomic percent; the subscripts refer to concentrations at phase mixture boundaries; VAA, VBB, and V,, are the bond energies between like and unlike adjacent atoms, respectively, at the interatomic spacing characteristic of the phase. The bond energies are usually assumed to be independent of small changes in the lattice parameter occasioned by solute additions and variations in temperature; V = VAB ---------------—— ; K(T) is the sum of the heat con- tent and heat entropy; R, the molar gas constant; and T, the temperature in degrees Kelvin. The free energy of a homogeneous phase is there- fore the sum of an internal energy, a specific heat, and a configurational entropy term, respectively. The compositions of two phases in equilibrium at a given temperature are governed by the minimum total free energy principle. Graphically, this is represented by the points of tangency of the tangent common to the free energy vs. concentration curves of the two phases. Analytically, this may be expressed as: ( df) = (df) [2] dc dc Expanding both sides using eq 1, the following equation is obtained after convenient readjustment of the terms: RT In[(ca)(1-c)]-½N (Vaa-Vbb)(Za-Zb) +NV [Za(l-2Ca)-Z,(l-2C,)] [3] The following assumptions have been made at this point: 1—The specific heats of the two phases are independent of composition variations within the range under consideration. Accordingly, the K(T) terms disappear on differentiation. 2— (Vaa)o = (VAA); (VBB). = (VBB); Va = V, Theyjustification for these assumptions can lie only in the successful application of the resultant equation. It may be noted that Zener2 has used assumption 1 in the calculation of the boundaries limiting the (a+j3) phase mixture in the Cu-Zn system.

Jan 1, 1952

By B. Wilshire, W. J. Evans

W. J. Evans and 8. Wilshire SEVERAL recent investigations1-6 have shown that the strain, c, during transient and steady-state creep is well-represented by the expression: € = e0 + et(l - e-mt) + Esl [l] where Eo is the instantaneous strain on loading, ET the total transient strain, C, the steady creep rate! and m a constant relating to the rate of exhaustion of transient creep. However, it has been noted6 that deviations from this equation occur over the first 10 to 15 pct of the transient stage, when the creep rate, (. decreases more rapidly than is predicted by this equation. This rapid decrease has been attributed to a large change in work-hardening coefficient. It 1s widely accepted that steady-state creep results from a balance between the rate of strain hardcning h and the rate of recovery r (=-s(st) as: dE/dt = Es = r/h [2] Comparison of values obtained for h at the end of the initial extension and during steady creep suggests that h increases several fold during the transient stage. which has the effect of reducing the creep rate proportionally.7 To examine the dependence, on r and h, of the deformation behavior during transient and steady-state creep. a series of constant-stress creep tests was carried out at 413°C at 6000 psi using 70-30 a brass. Prelinlinary investigation showed that. with this material. the transient stage constituted a significant portion of the total creep life (-0.4tf. where tf is the time to fracture). The alloy. obtained from Metals Research Limited. was made from high-purity copper, 99.999 pct. and zinc. 99.99 pct. Heat treatment at 675°C for 4 1/2 gave a uniform grain size of 5 mm-1. Details of specimen preparation and creep testing procedures have been given previously.6 Values of h (?s/?E) were determined by measuring the instantaneous strain. ?E. which occurred on increasing the stress during creep by a small amount. ?s. Similarly. v (= -?s/ ?t) was derived from the incubation period. At, after a small decrease in stress.&apos; Several values of v and h were obtained throughout duplicate creep tests. using different stress increments in the range 300 to 800 psi. The accuracy with which Eq. [I] represents the present creep curves was established by determining the best value of the constants Es, Et, m , and 6, using a digital computer program based essentially on the graphical solution for this equation devised by Conway and Mullikan.9 About 40 strain/time readings were taken during transient and steady-state creep. Over most of the creep curve, the average difference between the measured reading and the calculated strain at the appropriate time was less than 0.0001. However.

Jan 1, 1969

By Donald L. Katz, Leo B. Bicher

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896&apos;F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg&apos;7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944