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By W. F. Kieschnick, Eugene Harrison, W. J. McGuire

W. J. McGuire, et al, are to be commended for their undertaking of a mathematical solution of a very difficult problem. Unfortunately, however, a mathematical approach requires the application of several assumptions. These assumptions appear to be unrealistic and lead to answers which do not describe what actually happens when hydraulically fracturing oil and gas wells. Considering laboratory confirmation of breakdown phenomena, the authors appear to have tested their theories only on cement specimens and on samples of Austin limestone, much too small to provide any fracture system. This work resulted in the formation of vertical fractures. If the authors had tried similar experiments on thick walled cylinders made from almost any sandstone cores, they would have found that, using crude oil as the breakdown fluid, horizontal fractures would almost always occur, and at pressures much lower than any calculated. They would also find that by confining the fluid to within the bore (using oil base mud for example) on similar samples, the pressures required to burst the cylinders would be considerably higher and most of the fractures would be vertical. This breakdown pressure behavior has been duplicated in wells in Texas, Oklahoma, Kansas and in Wyoming. Considering field data the phenomena of different breakdown pressures for different breakdown techniques can be further illustrated. Most production and service personnel will agree that a breakdown can be more easily obtained if injection into a formation can be established prior to the occurrence of the breakdown. This is true whether the formation being treated is completed as open hole or as a perforated interval. This is clearly illustrated by a Lakota well in Wyoming, completed open hole at a total depth of 7,358 ft. An attempt to vertically fracture this well failed when a bottom hole pressure of 10,326 psi was insufficient to break down the formation. A non-penetrating type fluid (oil base mud) was in the well at the time the breakdown was tried." The oil base mud was then cleaned out of the well and replaced by a 30" API gravity crude oil. With this oil in the hole the formation breakdown was easily accomplished at a bottom hole pressure of 3,607 psi. This large difference in fracture pressures would be impossible according to the theories presented by McGuire, et al. The authors have used as an example the breakdown pressures experienced when acidizing Permian Basin wells. During acid treatments of limestone and dolomite the "breakdown" (drop-off in pressure) seldom occurs until some injection of acid has been accomplished. In these cases the breakdown is most likely to result from the chemical reaction of acid and rock in already existing vugs and fractures rather than from making a new fracture by hydraulic pressure. If this is true, then results in the Permian basin should not be used to validate the authors' calculations. *** AUTHORS' REPLY to ROSCOE C. CLARK and HENRY F. COFFER The purpose of our laboratory experiments in which thick-walled rock cylinders were hydraulically fractured was to determine the validity of the "thick pipe" formula for brittle materials, and not to predict nor demonstrate directly the orientation of field fractures. Our conclusions concerning field results resulted from calculations involving the "thick pipe" relationship as well as considerations of overburden stresses, rock strengths, and the geometry and dimensions of the field system. Clark suggests that had the models been more porous or contained weak bedding planes, horizontal fracturing would have occurred. This is undoubtedly true provided external stresses similar to those in the earth's crust are nor imposed. However, if we were going to design experiments to represent directly the field case we would impose the proper stresses on the models. It is generally recognized that the vertical compressive stress in the earth's crust arising from the weight of the overburden is approximately 1 psi/ft of depth. Then, as an example, even though a horizontal bedding plane has zero strength, the formation cannot be separated to form a horizontal fracture unless the hydraulic pressure exceeds the stress due to overburden. And in those cases in which the stress resisting vertical fracturing is significantly less than that resisting horizontal fracturing, vertical fractures should result, notwithstanding horizontal plane weaknesses. We agree that breakdown pressure will be less if the fracturing fluid penetrates the formation. In Appendix HI of our paper it is shown that leak-off reduces the pressure necessary to initiate either a horizontal or vertical fracture. It would be difficult to attempt to

Jan 1, 1955

Jan 1, 1908

By I. Fatt

Laboratory relative permeability data on reservoir rock are obtained on samples which are not subjected to overburden pressure during the permeability measurements. These data are then used for calculating the performance characteristics of reservoirs in which the rock is under the pressure of the overburden. Recent observations have shown that the permeability and porosity of reservoir sandstones are decreased by application of overburden pressure. These observations led us to a study of the effect of overburden pressure on the relative permeability characteristics of sandstones. A previous note from this laboratory1 showed that overburden pressure, simulated by applying hydraulic pressure to the outside of a plastic mounted core. caused a reduction in permeability of the core by as much as 50 per cent at 10,000 psig. In a multiphase fluid flow system, the relative permeability at a given saturation will change if the permeability or the effective permeability changes but not if both permeability and effective permeability change by the same ratio. The tests described in this note were made to determine the effect of overburden pressure on permeability and effective gas permeability in the gas-oil system. The gas-oil system was chosen because the available equipment was best suited for studying this system. The resultant data can be applied to other systems of interest because the gas permeability in the gas-oil system is the permeability of the nonwetting phase and, as such, is equivalent to the gas permeability in the gas-oil-water system and to the oil permeability in the oil-water system. EXPERIMENTAL METHOD Cylindrical test plugs, one in. in diameter and one in. long, were cut from sandstone core samples from three different reservoirs. After extraction in toluene, the plugs were mounted in Lucite by conventional core mounting methods.3 The core properties are given in the legend in Fig. 1. The mounted cores were machined to fit the apparatus shown in Fig 4. Air permeabilities as a function of overburden pressure were measured by connecting lines (1) and (2) to a conventional air permeameter. To measure porosity changes as a function of overburden pressure, the lines leading to (1) and (2) and the core were saturated with kerosene; line (1) was capped and a small bore precision calibrated pipet was connected to (2). Changes in pore volume of the core as overburden pressure was applied were noted by reading the amount of kerosene produced into the pipet. To correct for the change in volume of the lines inside the hydraulic cell as a function of pressure, a pressure-vs-volume run was made with a solid Lucite cylinder substituted for the core. The change in volume of the lines was about 10 per cent of the change in pore volume of the core. No correction was needed for the permeability measurements because there was no measurable pressure drop in the lines at the maximum overburden pressure. Relative gas permeabilities were measured by the stationary liquid method described by Osoba, et al.' Gas saturations were obtained by allowing the kerosene from a kerosene saturated core to evaporate out. This procedure was followed

Jan 1, 1953

By AIME AIME

IN an address before the New York Section. A.I.M.E., Oct. 20, Alex L. ter Braake, speaking on the tin industry of the Netherlands East Indies, interjected a few remarks, at the chairman's request. on the mineral stock-piling project now before Congress in a bill sponsored by Senator Scrugham. The full text of Mr. ter Braake's paper was published in the Nov. 6 issue of the American Metal Market. Following mention of the buffer stock scheme as applied in the tin industry, Mr. ter Braake continued:

Jan 1, 1943

By A. T. Shurick

WHATEVER the outcome of the Industrial Recovery Act, it has currently injected the first hope and optimism into the coal industry for more than a decade. Compared with the recent drab years the results are impressive: Bituminous production for the first ten weeks, 78,000,000 tons, may be compared with 63,000,000 last year; anthracite, 14,600,000 tons and 9,600,000 tons for the same periods, respectively, bringing the heaviest payrolls in ten years with individual checks reminiscent of former boom times. Hurried calls for long deferred new equipment and replacements have stimulated foundry and machine works and the -invigorating effect on the railroads is indicated by the first actual car shortage in a decade. And even in the welter of confusion over code prices, this heavy tonnage has moved at the most profitable figure the coal man has realized for many years, though with the large volume on old contracts, profits were not as large as many think.\

Jan 1, 1934

By V. I. Purcell, R. E. Snow, S. C. Sun

FATTY acids have been used as standard collectors for floating the matrix1-8 but not the leached zone phosphate ores. After a series of investigations, Davenport9 and Tarbutton10 concluded that the Florida leached zone ores tested were unamenable to fatty acid flotation and must be upgraded by floating the siliceous gangue with Armac-T as collector. The cationic flotation was estimated11 to cost almost ten times as much as a fatty acid process that would ideally give the same flotation grades and recoveries of phosphates. Mineralization: Extensive deposits of leached zone aluminiferous phosphate occur in The ore sample used for this work was obtained from the Virginia-Carolina Chemical Corp., Clear Springs area, Florida. The ore is a potential source of uranium and aluminum as well as phosphorus. Since the uranium and the recoverable aluminum are contained in some of the phosphate minerals, an upgrading of phosphate results in a corresponding enrichment of both uranium and aluminum. The phosphate minerals in the ore are primarily pseudo- wavellite, millisite, and carbonate fluorapatite, with a minor amount of wavellite. Quartz and clay are the common gangue minerals, quartz being pre- dominant. Others present in small amounts are ilmenite, hydrated iron oxides, staurolite, monazite, and zircon.

Jan 1, 1957

By Lloyd Jones

THE strip industry made rapid strides in regard to both width and gage until about 1922, when the maximum width was about 20 in. In the hot mills, strips of thin gages in wide widths could be pro-duced, but only at a sacrifice of length of coil, con-siderable increase in power, and decreased tonnage out-put on the min. Hot mills, like the Bray sheet mill and the modern strip and skelp mills, demonstrated that . wider strip could readily be rolled, if such a product was desired. The strip manufacturers were really limited in width, not by the hot strip, but by the cold rolling of wide strip. This factor was roll pressure. The diameter of rolls increased as the width of strip increased. For cold rolling strip 20 in. wide, cold rolls were approximately 20 in. diameter. As the rolls became larger, the arc of contact between the rolls and the strip increased approximately, according to the formula, b=\/Rd where b = the width of contact R = roll radius d = total reduction Now the crushing strength of cold steel of low carbon varies from 70,000 to 100,000 lb. per sq. in. With each succeeding pass the crushing strength increases and may approach 250,000 lb., according to the total reduction. The total reduction in cold rolling of low-carbon steel will range from 40 to 70 per cent of the original thickness, usually in about three or four passes. On this basis, assuming a reduction of 20 per cent in one pass, the crushing strength of steel assumed at 120,000 lb., we have a total pressure between rolls, which (assuming that the rolls do not deform) equals: Roll Strip Strip Diameter, Width, Thickness, In. In. In. Pounds 10 10 0.100 380,000 20 20 0.100 1,080,000 30 36 0.100 2,375,000 42 50 0.100 3,900,000 These figures are approximate, but you will note that in increasing the width five times, or 50 in., the total pressure between the rolls increased approximately ten times. In other words, the pressure per inch of width increased from 38,000 to 78,000 lb. for the same per-centage of reduction.

Jan 3, 1928

By H. M. Howe

It is a grave objection to the present system (or rather lack of system) of mineralogical nomenclature that, in the very great majority of cases, the name of a mineral gives no hint of its chemical composition, one might almost say no suggestion, however faint, of anything connected with it or characteristic of it, chemical, physical, historical, geographical, geological, or lithological. In becoming acquainted with a mineral, in addition to learning its composition and important characteristics, one must also learn a name wholly unconnected with any of them. It has occurred to me that a system might be devised in which the name of each mineral should express at least an approximation to its ultimate composition. It is far easier to learn the names of most minerals than their compositions. Most of us are familiar with the names and appearance of many minerals, especially among the silicates, of whose compositions we have but a rough notion. It would be the aim of such a system to enable us, in making the one slight effort of learning the name of a mineral, by that same effort and involuntarily to learn its composition, which now requires an additional and a much greater effort. I have worked out a system designed to meet this requirement, and its description occupies the remainder of this article. Doubtless there are many devices on which could be based other systems fulfilling the requirement above set forth better than that about to be described does, and at the same time furnishing names

Jan 1, 1884

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

By George I. Adams

A party, consisting of George I. Adams, of the United States Geological Survey, A. H. Purdue, of the University of Arkansas, and Ernest F. Burchard, was engaged, during the summer of 1902, in the study of the zinc- and lead-deposits of Northern Arkansas. An extensive report on this field is now in preparation. The following preliminary statement of results and conclusions is made in advance of the final publication, which will be accompanied by detailed geologic maps and other illustrations and a fuller treatment of the subject. Location.—The Northern Arkansas field embraces Marion county and adjacent portions of Boone, Baxter, Newton and Searcy counties. Outside of this area there are a few scat tered mines, notably in Sharp and Lawrence counties. The mining development lies north of the Boston mountains, in what is known as the Ozark Plateau. The country has a broken surface, as a result of dissection by streams, and there are numerous exposures of the mineral-bearing horizons in the valley slopes. This has greatly facilitated prospecting. History.—Lead-ore was discovered in Northern Arkansas by the early explorers and pioneers, and at first was utilized for rifle-ballets. Later, it attracted considerable attention, and in the '50's was smelted in the vicinity of Lead Hill. There was a revival of the industry during the "70's, but the cost of transportation was so great that it was practically abandoned. Zinc-ores at first attracted little attention, probably because they were not so well understood. Before the Civil War, however, some zinc was smelted. In the '80's, prospecting was carried on generally throughout the field, and resulted in finding zinc at so many places and so readily accessible that

Jan 1, 1904

By B. E. Lindsly

The withdrawal of gas and/or oil in appreciable quantity from a natural oil reservoir causes the pressure within the reservoir to diminish, and if the oil is completely saturated with gas, this dissolved gas begins to evolve from solution. The liberation of gas from solution in oil causes the oil to change in several ways, the principal changes being: (1) reduction in volume or "shrinkage"; (2) increase in specific gravity (decrease in degrees A.P.I.); (3) decrease of energy in the oil; (4) increased viscosity; (5) increased surface tension. As the writer's investigations have been concerned more with the first three items than with changes in viscosity and surface tension the following discussion relates particularly to the volumetric shrinkage of the oil, to the increased specific gravity, and to the decreased energy in the oil, each caused by the liberalion of dissolved gas. One of the most surprising facts that have developed in the study of high-pressure well-head and "bottom-hole" samples is the great reduction in volume that occurs in some oils when the naturally dissolved gas is liberated. High-pressure samples taken from well heads in the Oklahoma City, Kettleman Hills and Ventura, Calif., fields decreased in volume from 11.2 to 40.5 per cent when the dissolved gas was liberated in reducing the pressure on the sample to atmospheric. The amount of shrinkage an oil undergoes when gas is liberated depends upon the quantity of gas liberated and also upon its composition. A given volume of the heavier gases, propane and butane for example, will occupy more space in the oil than an equal volume of methane. The reason for this probably is that the molecules of the heavier gases are larger than those of the lighter gases. When gases are not in solution, and particularly when they are at low pressures, the distance between the gas molecules is so much greater than the dimensions of the molecules themselves that the mere size of the molecules has little effect upon the space occupied by the gas, Avogadro's hypothesis, which in effect states that all gases under the same conditions have the same number of molecules per unit volume, relates to this phenomenon. The fact that the heavier gases occupy more space than the lighter gases in the oil, and

Jan 1, 1934

By Newell Alford

AT its meeting in the fall of 1937, the Executive Committee of the Coal Division considered the growing scarcity of young engineers entering coal mining with serious intentions. This scarcity was the cause of con-siderable alarm and a committee consisting of C. T. Hayden, E. A. Holbrook, C. E. Lawall and L. E. Young, with the writer as chairman, was appointed to gather factual data on the current trend. A questionnaire1 was designed and mailed to the heads of the 60 mineral technology schools listed by Prof. W. B. Plank in his article in September 1937.2 Replies were received from 46 institutions, not all from heads of coal-mining courses but all from men that at one time or another have had experience with some kind of coal-mining curricula and know current student impressions. Our committee is indebted to all of these gentlemen for their cooperation. Our committee hoped by this means to quickly reach the root of the trouble and make a set of comprehensive recommendations to the Coal Division for relieving the industry immediately from the growing dearth of youth who yearn for coal-mining careers, but the condition is more serious than at first diagnosed. We must now refer the question back to the Coal Division, with the recommendation that the Division get the industry's permission for still another major operation on its frame of mind. In addition to 10-year statistics on the first pay received by graduates in coal mining and other technical work, we requested enrollment data for 20 years from all schools with either mining engineering or mineral technology curricula. Nine leading questions were also plied, as shown in the Appendix. Every one of the answers was significant and inter-esting. Fortunately, we encountered positive frankness that was extremely helpful.

Jan 1, 1938

By Ralph Sweetser

IN these days of the almost exclusive use of byproduct coke as the blast-furnace fuel in this country, it may seem out of place, and smacking too much of reminiscing, to say anything about the use of anthracite coal for blast-furnace fuel. Viewed in the light of present day research and of developments in alloy steel, some observations seem appropri-ate regarding this raw material that played such an important part in the development of the iron and steel industry during 50 years of the past century. The research work of that period, in which the whole iron and steel industry was revolutionized, passing from wrought iron to steel and from charcoal to three new mineral fuels for blast furnaces, was done chiefly in the full-sized plants of that day; and it was done largely by the ironmasters themselves. The laboratory had not become a part of the ironworks, and scientific instruments were lacking around the blast fur-naces; "rule o' thumb" and erroneous theories prevailed-and have not yet all been eliminated. The recent interest in meteoric iron in connec-tion with nickel steels and other alloys proves that it is worth while to search for the reasons for excellence and the causes for failures in the metallurgy of bygone days. Turner1 gives the reasons why the blast furnace of Dr. F. W. Geissen-hainer on Silver Creek, Schuylkill County, Pennsylvania, about 10 miles northeast of Pottsville, was operated successfully with anthracite2 in August and September, 1836, and why several other attempts failed. It has taken a long time for us to find out that there are great differences in the behavior of anthracites from the several parts of the anthracite region, as well as differences in coking coals from the bituminous fields.

Jan 1, 1935

By Charles O. Thomson

When a wire rod of iron or of steel is immersed in a hot solution of common salt, allowed to remain long enough to bring the metal to the temperature of the brine, and withdrawn, the surface of the rod is irregularly covered with a deposit of crystals of salt. These crystals adhere to the cod with great firmnes, in consequence, doubtless, of a thin film of ferric hydrate, which is formed between them and the rod as the water dries off. The rod can now be reduced, by successive passes through a dic or draw-plate, without any

Jan 1, 1881

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400' or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400' or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By Francis M. Walters, Irvin R. Kramer

THE substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient of expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and [ ] their use up to 400° or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. EXPERIMENTAL METHODS Two methods were used in studying the stability of the low-expansion iron-nickel-cobalt alloys. Dilatometer specimens were held at 480°C, for 9 months and the change in expansion characteristics was determined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection [ ] temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1941

By Francis L. Sperry

Up to within a few years, the consumption of nickel has been more directly dependent upon the available supply than that of any of the other useful metals. The Gap mine, in Lancaster county, Pennsylvania,* has been, for the last quarter of a century, the only property in this country furnishing nickel in paying quantities. Its yearly output was about 300,000 pounds of metallic nickel, or nearly half the amount used annually in the United States. Foreign nickel from mines on the New Caledonia islands, in the South Pacific, found entrance into our markets as the production of the Gap mine fell off. The price of nickel was constantly maintained, and no special effort was made to extend its use. Over-production was cautiously guarded against, and all surplus metal was held by the banking-houses of the Rothschilds, who assumed the bonded indebtedness of the Sociètè le Nickel. The opening of the Ontario nickel-mines has, however, brought about a radical change; and nickel from the Sudbury district can be delivered in New York within four days, and in European markets within two weeks, as against two months consumed in transporting South Pacific ores. Former prices have been irretrievably smashed, and European trade-journals comment favorably on the influence which Canadian nickel has had in making lower prices, and breaking the backbone of the " nickel trust." Production and Costs. The quantity of nickel produced and the prices which it commanded may be briefly summarized as follows: The total production of the world from 1840 to 1860 was about 100 to 250 tons yearly of metallic nickel; from 1860 to

Jan 1, 1896

By L. D. Hall, S. J. Rothman

DIFFUSION coefficients of RaD (PD) and RaE (Bi) in a Bi-0.255 atomic pct Pb alloy have been measured by the methods outlined in a previous paper.' The following changes were made in the experimental procedures: the bath was made up of about 400 to 500 g Bi; and no correction was made for the volume change of bismuth on melting. The data are presented in Table I and Fig. 1. A least-squares analysis of the data yielded D = (0.120 t 0.09) exp ( -9680 + 1070/RT) D- (0.0465 0.001) exp (-8100 + 466/RT). Statistical analysis of the data indicated that the activation energies are significantly different at the 50 pct level, but not at the 75 pct level, while the D values are significantly different at the 97.5 pct level, but not at the 99 pct level. The differences are thus not as clear-cut as they were for lead. However, bismuth diffuses faster than lead in high bismuth alloys as well as in lead. The high activation energies, more than twice the value calculated from viscosities, are in good agreement with the results of Grace and Derge.' No data were obtained at higher temperatures because of gas bubble formation in the capillary. Acknowledgments This work was supported by the Office of Ordinance Research under contract DA-04-200-ORD-178. The authors thank 0. P. Vieria and M. Volpe for help in the experimental work.

Jan 1, 1957

By R. H. Dourson, B. H. Sage, W. N. Lacey

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943