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By G. A. Moore, D. W. Williams, C. E. Sims

During the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging, The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary ab- normal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. I, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. 'The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.' Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period of approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the System could be degassed thoroughly in

Jan 1, 1949

By G. A. Moore, D. W. Williams, C. E. Sims

During the past several years, the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture, and the ductility values can often be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging. The cure of such an abnormal condition represents a real improvement in the quality of the steel. Several types of abnormal loss of duetility can be distinguished, of which those caused by excessive amounts of inclusions of undesirable type and those caused by unsuitable grain size and inget structure are well known. The particular type of abnormal lowered ductility currently under consideration may be distinguished by the fact that the low-temperature aging treatment necessary for its relief is insufficient to cause any visible change in the micro-structure as ordinarily observed. As this aging will in fact eventually occur at room temperature, the phenomenon of present interest may be given the symptomatic definition, ''Temporary Abnormal Low Ductility." Some hundreds of previous investigations, largely qualitative in nature, have established, beyond reasonable doubt, that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary abnormal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, The Steel Founders' Society of America has, since Nov. 1, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-duetility effects and porosity. The interest of this investigation thus extends to permanent abnormal losses of ductility, such as are caused by the inclusions which sometimes result from special deoxidizing practices and possibly from metallic nitrides, but as these can he distinguished from the temporary effect of hydrogen, they have been excluded from the work reported here except when they

Jan 1, 1949

By Lo-Ching Chang, K. M. Goldman

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By R. W. Hyde, S. E. Eaton, B. S. Old

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides' In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By C. W. Binckley, F. R. Burgess, E. R. Haymaker

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well's actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2'' O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

By Owen Thornton

Recently equations have been presented by Rose and Bruce&apos; and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"&apos; multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately&apos;: — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

Jan 1, 1949

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By M. W. Bartley, Hugh M. Roberts

Substantial deposits of Bessemer hematite have been found recently by drilling beneath Steep Rock Lake, Ontario, which is situated in the northern part of the Lake Superior Region. It will be practicable to divert the waters flowing into this lake and develop open pits on the upper pert of two large ore bodies by damming off and pumping out the water in the part of the lake in which they occur. Ultimately, the bulk of the ore will be mined by underground methods. Owing to the generally massive nature of the rocks in the area, no underground flows of major consequence are anticipated after diversion of the lake. The Steep Rock deposits are attributed in origin to hydrothermal replacement. They were formed, for the most part, along an unconform-able, brecciated contact between the Steep Rock limestone and an overlying younger volcanic series, The replacing solutions came in as igneous after-effects, following upon the intrusion of basic igneous rocks that invaded the hanging-wall volcanics. It is believed that this took place in a geological period roughly equivalent to late Middle Huronian, which was the period when the most extensive iron-bearing rocks of the Lake Superior Region were formed. Comparison is made with other deep-seated iron-ore bodies in the Lake Superior Region, the origins of which are ascribed in the discussion to hydrothermal replacement. Introduction Under the waters of Steep Rock Lake, Ontario, situated on the Canadian National Railway, 142 miles west of Port Arthur, the presence of three ore zones containing red and brown Bessemer hematite has been established. These were discovered and have been partly explored by means of diamond and churn drilling, The positions of the ore zones, designated as A, B and C, are shown on the accompanying maps and cross sections. This exploratory work, begun in 1938 by Joseph Errington* and Julian G. Cross, has been carried on by Steep Rock Iron Mines Ltd., and was continued during the winter of 1941-1942. For more than 60 years explorers have known that large quantities of hard hema. tite float of good grade existed along the south shore of Steep Rock Lake, and the presence of ore beneath the lake was inferred by many early geologists and explorers. Despite numerous previous attempts to find ore in place, actual discovery awaited the recent period of intensive exploratory effort in Canada. The results obtained in the drill holes put down since 1938 by steep Rock Iron Mines Ltd. are not only of interest, in themselves, to those concerned with the development of ore deposits, but, taken in connection with the surface exposures of adjoining formations, they form the assemblage of facts from which the geological reasoning in this paper proceeds; accordingly, they are set out here as briefly and exactly as may be.

Jan 1, 1949

By Robert C. Stephenson

Large deposits of titaniferous magnetite occur associated with anorthosite and gabbro in the Lake Sanford area, Essex County, New York. The ore, gabbro, and anortbosite show consanguineous relations. Anorthosite grades through gabbroic anortbosite into gabbro but is locally intruded by gabbro. Structural and petrographic evidence suggests that gabbro was differentiated from anorthosite by filter pressing. Field and laboratory study of ore occurrences indicates that an ore residuum concentrated in the gabbro through magmatic segregation&apos; by normal crystallization and flowage. Ore occurs as bands which grade into gabbro, and also as large masses which replace anorthosite. Ore in the gabbro is finer grained and richer in ilmenite than ore in anorthosite. Introduction The Lake Sanford area lies in the heart of the Adirondack Mountains, in the southeast portion of the Santanoni Quadrangle (Fig. I), and there are four ore bodies in the area immediately surrounding Lake Sanford. The area lies 30 miles by highway from the railroad at North Creek. The deposits were discovered in 1826, and from then until 1858 iron was produced in small quantities. They were idle from 1858 to 1906. Between 1906 and 1913, extensive development work was carried on. These early attempts to produce iron ore were thwarted by transportation difficulties and by the titanium content of the ore, which, ironically, has been the element responsible for the present development. In 1941 the National Lead Co., Titanium Division, developed the Sanford Hill ore body and is now producing ilmenite and magnetite concentrates.18 The Defense Plant Corporation is extending the railroad to the property from North Creek and is building a sintering plant to treat the magnetite concentrate. Investigations OF the Deposits* Early studies of the Lake Sanford titaniferous magnetite deposits were made by Emmons in 1842,l2 by Kemp, in 1897-98&apos;0 and by Newland in 1908.22 Singewald26 and Osborne23 considered these deposits along with numerous other titaniferous magnetite deposits in 1913 and 1928, respectively. None of these reports entailed a detailed study of the ore occurrence in this area. The present study was begun in 1940. Seven months were spent in the field, and considerable time was spent in labora-

Jan 1, 1949

By F. H. Kihlstedt

The Larap iron deposits, 125 miles east of Manila, are the biggest high-grade iron deposits in the Philippines, and have in seven years produced nearly 4 million tons of 60 per cent ore. Magnetic surveying followed by churn and diamond drilling cheaply developed a score of million tons. The ore zone is a wedge of metamorphic rocks in fresh, Miocene sediments overlain by agglomerates, which seem to have filled a river valley eroded in the sediments. A mild overthrust of the competent agglomerates crumbled the shale in front. Solutions gradually turned it into more competent hornfels and deposited pyrite, then magnetite and pyrite in the pores. As the temperature rose large bodies of magnetite with some pyrite were deposited by replacement and in open cavities in tensional areas of overthrust shears. At still higher temperature magnetite and calcium-magnesium silicates formed other bodies in similar cavities, and finally the thrust zone was invaded by syenite porphyry, causing high-temperature alteration products. Possibly, as temperature abated, more high-grade ore was deposited. The complicated faulting indicates dynamic, chronological and spatial changes of mineralization rather than zoning in a static system. Noncommercial copper, molybdenum and some gold accompanied the iron mineralization. In the thirties the Philippines gained a justified reputation as a country of considerable mineral wealth. Traces of Chinese workings show that these earliest travelers and traders had in a small way exploited the latent gold resources in the Islands. The Spaniards continued this for centuries, but did not succeed in establishing any steady mining industry. Modern technology was required to get it started. The rapid development in the last decade before the war got its impetus from several financial factors, the return to sugar growers of previously collected taxes, the influx of Spanish capital during the civil war in Spain, the influx of Chinese capital when the Japanese started their "China incident," and others. Directly or indirectly much of this capital reached the mining industry; in particular, gold mining. Out of the turmoil of an exceptional mining boom emerged a sufficient number of good and well managed gold properties to send the production to a level above that of any single state in the United States at the time. Other ore deposits besides those of gold also received their share, and for a country without any heavy industries at

Jan 1, 1949

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:&apos; On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron &apos;re, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been &apos;designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By John W. Vanderwilt

The fluorescence of scheelite has been an important aid in recent years in the discovery and development of scheelite deposits. The use of fluorescence of synthetic compounds in industry, particularly in advertising, also has expanded greatly during the past decade. As a result, a number of new and convenient units for producing ultraviolet energy have become available, which have led to a greater application of fluorescence in the study of minerals. Studies have shown that the fluorescent color of a mineral may vary: (I) with the kind and quantity of trace elements, and (2) with the particular wave length of ultraviolet energy used. The wave length is dependent first on the type of generating equipment used, and finally on the filter employed to remove the visible light that may be present. A number of so-called ultraviolet lamps are listed and described, together with suitable filters known to be available. Scheelite fluoresces brilliantly with wave lengths of 2200 to about 3000Å., but not with longer wave lengths. The most convenient and efficient sources of ultraviolet for scheelite fluorescence are portable and laboratory units designed particularly for use with scheelite. So-called ultraviolet light globes of the photo-flood type emit wave lengths too long to cause scheelite to fluoresce. Attention is called to the minerals that fluoresce in a manner similar to scheelite, which necessitates a check test by means of characteristic physical properties. Chemical tests are the final authority both for identity and content of tungsten in scheelite ore. Introduction Recent development and extensive use of fluorescent lighting make it unnecessary to explain what fluorescence looks like. The fluorescent light tube is in reality a mercury vapor arc, which generates ultraviolet energy. Coating the inside walls of the tube is a substance, called a phosphor, that converts the ultraviolet rays to visible rays of light. In a like manner, certain minerals will transform ultraviolet energy to visible rays of various colors. The phenomenon of brilliant fluorescent colors cannot be satisfactorily described or reproduced photographically; a display must be seen to be appreciated. Only a few years ago fluorescence was regarded primarily as a source of entertainment, chiefly in spectacular displays of specimens in museums. The brilliant fluorescence of willemite, a zinc ore mineral, at Franklin, New Jersey, was utilized quite early in checking the efficiency of certain milling operations. Fluorescence has been used extensively in exploring for scheelite, as well as in mining this ore, during the past 10 years. The use of fluorescence in detecting scheelite, an important tungsten ore mineral, is well established, and much success has attended this new method; scheelite is a very inconspicuous white to gray mineral in ordinary light, but it

Jan 1, 1949

By H. L. James

This paper presents the results and analysis of field trials of various magnetic instruments over anomalies ranging from 20 to 5000 gammas of vertical intensity. The following instruments were used: Askania vertical magnetometer, Wolfson vertical magnetometer (model M-I), Hotchkiss Superdips (used both parallel to and normal to the magnetic meridian, with several settings of the "sigma" angle), Lake Superior dip needle, and the dipping circle for measurements of inclination. The change in inclination over the measured anomalies ranged up to 4"; this caused pronounced changes in sensitivity of the Hotchkiss Superdip oriented parallel to the magnetic meridian. The variable sensitivity not only gives apparent displacement of crests of anomalies, particularly at high sensitivities, but also makes the data difficult or impossible to use in preparation of iso-anomaly maps. This weakness in field performance of the Superdip is shown to be eliminated by orienting the instrument normal to the magnetic meridian and measuring vertical intensity only, which in the latitude of upper Michigan is equal to 97 pct of the total intensity. The dip needle is seen to be relatively ineffectual for location of anomalies of less than 400 gammas. Introduction The U.S- Geological Survey, in cooperation with the Geological Survey Division of Michigan Department of Conservation, has for the past three years been engaged in a restudy of the Iron River-Crystal Falls iron mining district of upper Michigan. The bedrock in a large part of this area is covered with glacial deposits as much as 500-ft thick, and, inasmuch as some of the rocks have moderate to high magnetic permeability, extensive magnetic mapping has been done to assist in unraveling the complicated structure of the area. Several types of instruments have been used, and the major purpose of this paper is to present comparative data on the field performances of some of these instruments so as to aid others who face similar problems elsewhere to evaluate and choose the instruments best suited for the work. The paper is directed primarily to geologists and engineers rather than to geophysicists, although some familiarity with the instruments is presumed. The geology of the area consists of a complexly folded series of weakly metamorphosed sedimentary rocks, including the iron formation, which rests on older greenstones. Although the iron formation itself is only locally magnetic, some of the beds stratigraphically above the iron formation are rather strongly so. By tracing these hanging wall magnetic anomalies valuable information is obtained from which the structure and distribution of the iron formation can be inferred. Critical anomalies range from 25 to 6000 gammas of vertical intensity. Many anomalies can be traced in part with the common dip needle, but detection of others requires more sensitive instruments.

Jan 1, 1949