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By Arthur Boynton

IN THE preparation of this paper the writer has been influenced by the fact that descriptions of various means of cleaning blast-furnace gas have been published and that further descriptive treatment of the subject will probably be less interesting than a statement of conclusions with regard to preferable methods which have been reached by him as a result, of experience and observation in this country and also as a result of somewhat detailed investigation of the subject made toward the end of the year 1927 on the Continent of Europe and particularly in. Germany. Owing to various circumstances, including a cost of fuel that is extremely high in relation to the wages of labor, the German iron and steel industry has accumulated experience in gas washing which is as yet in part lacking in the United States of America. The paper begins with a statement regarding the economics of the use of blast-furnace gas, then considers the principle's and practices employed in its purification. USES OF BLAST-FURNACE GAS For many reasons having to do with the utilization of coke-oven and blast-furnace gases in steel manufacture and with the use of hot metal, the blast furnace is now usually a part of a steel-producing unit, which also includes coke plant and rolling mill. Therefore both blast-furnace and coke-oven gas are usually applicable to any of the iron and steel-making processes, including the generation of power, and their allocation in any given works should be considered as a single problem. The uses to which blast-furnace gas, either alone or mixed with coke-oven gas may be put, include the following: Regenerative Heating of Air for the Blast Furnace.-This is the oldest and metallurgically the most important of all uses. It is universally performed with unmixed blast-furnace gas and under proper conditions should require not over 23.5 per cent. of the total gas generated for a blast temperature of 1350° F. For Steam-raising Purposes.-This is almost universally done with unmixed blast-furnace gas. From the standpoint of quantity used, it is at the present time the most important application in American steel-works practice.

Jan 1, 1928

By T. J. Koppenaal, M. E. Fine

A yield point effect attributed to short-range ordevi?g (SRO) occurs in Cu base Al. At at 296°K varies with heat treatment, decreasing as the annealing ternperature is raised .from 433Oto 598°K. Davies aid Cahn' observed a corresponding decrease in SRO. (523 °K anneal, measured at 77°K) is approximateZy proportional to the variations of A7 with strain rate and testing temperature are also Consistent with the idea that is associated with SRO. A preliminary investigation of the tensile properties of a Cu-Al single crystals showed the presence of a rather strong yield-point effect (drop in flow stress after initial yielding). The object of this research was to investigate its origin and behavior. a Cu-Al alloys are particularly interesting because diffuse X-ray scattering measurements by Davies and Cahn,' Houska and Averbach,' and Borie established the presence of short-range order. The degree of local order may be changed with heat treatment.' cottrel14 suggested that the presence of local order might result in a yield-point effect, and thus the possibility exists here for experimentally ascertaining the importance of short-range order with respect to yield points in these alloys. Since a 12 pct difference exists between the atomic sizes, elastic or Cottrell locking5 must also be considered. Further, Howie and swanne have shown that the stacking fault energy of copper is reduced by aluminum additions. The width of extended dislocations should thereby increase. hus the conditions appear attractive for Suzuki locking.' Finally, the possibility of stress-induced order at dislocations, schoeck locking,' must also be examined, EXPERIMENTAL PROCEDURE Alloys up to 14 at. pct Al were prepared by induction melting high-purity (99.999 pct) Cu and (99.996 pct) Al in a graphite boat under a dynamic vacuum of 5 X 10o mm of Hg. After homogenizing the ingots at 900°C for at least 24 hr under vacuum, they were rolled with intermediate anneals to strips 1.55 mm thick. Single crystals 10 in. long were grown by lowering strips, contained in a split graphite mold sealed in fused quartz at 5 X lo-' mm of Hg, through a single coil induction heater at a constant rate of 1/2 in. per hr. Tensile specimens 1.25 in. long were cut from the single crystal strips and reduced cross sections about 0.7 in. long and 3.0 to 3.5 mm2 in area were introduced by filing and abrading.8 To remove the worked portion about 10 pct of the cross-sectional area was removed by etching. Back-reflection Laue photographs of a filed and etched specimen were taken before and after annealing at 900°c for 24 hr. Small, well defined Laue spots were obtained with no visual difference in the two photographs. Further, specimens with and without the reduced sections began yielding at about the same stress. Hence, for our purposes, filing and abrading did not affect the structure of the specimens. Each single crystal specimen was annealed at 900° c in vacuum for at least 24 hr and furnace cooled; while cooling through the range of 250o to 200°c, the rate was about 55°C per hr. Orientations were determined by the usual back-reflection Laue

Jan 1, 1962

By Hans Lundberg

AFTER the war years, great activity has been shown in geophysical exploration for ore. The appreciation by mining and government geologists of geophysical techniques and results is largely responsible for the popularity of these methods. In Canada, plans are being made to study, by geophysical methods, the structure of a portion of the Pre-Cambrian shield in the hope that such studies will not only give a clearer picture of the geology, but will be of direct aid to the mining companies when selecting areas for detailed prospecting. Although geophysics thus has become more popular, some engineers are still reluctant to employ the methods to their full extent. Allotted funds are often rather low, so that the least expensive

Jan 1, 1947

By B. L. Averba

THE determination of retained austenite by X-ray diffraction uses the following relationship:"" Pa = constant . RVaA (8) [1] where: P is the diffracted power from phase a; R, the calculated intensity factor; A, the absorption correction; 8, the diffraction angle; and Va, the irradiated volume of phase a For a flat sample making a glancing angle + with the incident beam the absorption correction is calculated as: * 1 sin (28 - 4) A .= 1 [2] µ sin, (28 — 4) + sin 4 where µ is the linear absorption coefficient. Beu3 has proposed that the computed absorption correction be combined with the constant and that the experimental observation of the absorption correction used in the original method be eliminated. This procedure is permissible only if: 1—There is no preferred orientation in the sample, and 2—The geometric requirements have been met precisely. If these conditions are not met the validity of the determination is questionable. Unfortunately the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2. In practice it may be convenient to plot P/R vs the parameter sin (2? — )[sin (28 — +) + sin +] to obtain straight lines for the ap- parent absorption correction. Deviations from straight lines indicate either that the sample has not been positioned correctly or that the relative intensities are incorrect. Geiger counter spectrometer methods also have been used successfully for retained austenite determinations. In the usual spectrometer arrangement the sample makes equal angles with the incident and diffracted beams (8 = ); thus the absorption correction is simply 1/2µ and independent of 8. The retained austenite is then easily calculated from integrated intensity measurements on austenite and martensite lines. If the austenite content is not too low and if excessive fluorescence is not encountered it is possible to use filtered radiation and a recording spectrometer. The integrated intensities are then proportional to the areas of the diffraction peaks. For lower austenite contents the following technique was used: A bent quartz monochromator and a Geiger counter spectrometer are employed. The monochromatic radiation is focused on the front slit, and the counter slit is made broad enough to include the entire line. A series of readings are taken in the vicinity of the diffraction peak. The highest reading includes the diffraction line plus background. The background is obtained from the average of several readings on each side of the peak. The integrated intensity is obtained by subtraction. CrK, and FeKa have been used for such determinations. This technique has been found to be as sensitive and as accurate as the photographic methods. In the spectrometer methods the ratio austenite/ martensite may be obtained from readings on austenite and martensite lines and the application of Eq. 1. It is also possible to use external standards and to obtain the austenite contents from measurements on the austenite lines alone. The small correction for carbides then becomes unnecessary. The best standards are probably samples with known

Jan 1, 1954

By Carolyn Barnes

The Offshore Technology Conference, the world's largest technical conference and exhibition on the development of offshore resources and protection of the ocean environment, is sponsored annually in Houston, Texas, by 12 international engineering and scientific societies. This year's OTC, the seventh, will be held May 5-8 at the Astrodomain, and will be the largest in its history. The technical program for the first meeting in 1969 consisted of 100 papers, an exhibit display of 380 booths, and an attendance of 4300. This year. 280 technical papers are to be presented, and more than 2800 exhibit booths, representing some 1200 companies and nine countries, will be on display for an anticipated audience of 40,000.

Jan 4, 1975

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By O. D. Gonzalez, R. A. Oriani

The migration of hydrogen and of deuterium dissolved in a iron and in nickel induced by an applied electrical potential has been measured over a range of temperature. In all cases the intevstitial solute migrates to the cathode. The deduced charges of transport are positive, independent of or slightly dependent on temperature, and markedly larger for the beavier mass. These results are interpreted as showing predominating momenlum transfer between electron holes and the acticated complex of the elementary diffusion act. THE migration of components of a metallic system under the action of an applied electrical potential is called electromigration or electratransport. This phenomenon has been known since 1861 and is becoming of increasing interest to metal scientists because of the opportunity it offers to explore the connections between mass transport and electron transport. Until recently, reliable data have been very scarce because of the difficulties inherent in the measurements. In addition, theoretical understanding has been either nonexistent or rudimentary and at present this situation is only moderately improved. Whereas the prevalent notion had been (and is still widely held) that electromigration directly reflects the state of ionization of a component in its equilibrium state in the metal, it is now becoming clear that the major, if not the sole, factor is the momentum transfer between the charge carriers, themselves in motion because of the applied field, and the metallic components in their activated state. It becomes important therefore to obtain reliable data over a range of temperature on electrornigration in systems where only one component moves, that is, either in pure metals (vacancy motion) or in interstitial solid solutions. Our choice of systems was dictated by our measurements' of the Soret effect in solid solutions of hydrogen and deuterium in iron and nickel. Indeed, the main reason for making measurements on electromigration at all is that we suspected a mechanistic connection between thermal diffusion and electromigration. In our former paper' we proposed that what is common to both phenomena is the momentum transfer between the charge carriers in the metal and the atom as it jumps from one equilibrium position to another. In Soret diffusion, however, there is in addition the dissipation of the energy of the jumping atom via pho-nons. We have since found that similar ideas for this interconnection have been developed by Fiks.2 In the present paper we will discuss in more detail our understanding of the mechanism of electromigration itself, but we turn first to a presentation of the experiments and results. EXPERIMENTS AND RESULTS Let us consider a metallic system in which only one component, m , can diffuse at the temperature in question, and to which are applied simultaneously an electrical potential gradient, grad cp, and a chemical potential gradient, grad p,. One may write3 for the material flux Jm and the electronic charge flux Je by applying the condition, grad = 0, to Eq. [I] and evaluating grad(um/T) for the isothermal case and for activity coefficient independent of composition over the relevant composition range. ere, c is the concentration and D the diffusivity of the mobile component. The experimental technique that we have used to measure Z* for the isotopes of hydrogen individually dissolved in each of two transition metals has been developed from a method used by Wagner and Heller.4 (A somewhat similar method was also used by Herold.5) A wire or thin rod of the metal under study connects two volumes of gaseous hydrogen at identical pressures; hence grad um = 0. A direct current is made to pass through the specimen, serving to maintain the specimen at the desired temperature and also to produce the electromigration of the hydrogen dissolved in the metal in equilibrium with the gaseous hydrogen. Under these conditions, the flux of hydrogen from one volume to the other is given, from Eq. [I] for grad( um/T) =0by

Jan 1, 1968

By H. C. Heard

The review by Professor J. C. Jaeger (Chapter 1) briefly summarizes and discusses a select group of papers by various workers dealing primarily with aspects of fracture in brittle rock materials. Professor Jaeger's treatment is primarily concerned with the correlation of phenomenological and theoretical failure criteria with empirical results from short duration tests at ambient temperatures and generally at low lithostatic and interstitial fluid pressures. As engineering rock mechanics becomes more concerned with new techniques of mineral exploration and production at increasingly greater depths in the crust, it is well to be aware of the effect of the environment -that of the superposed stress field upon the lithostatic and interstitial fluid pressure, the temperature and the duration of the loading upon the failure of rocks either by fracture or flow. All results to be discussed here are from laboratory tests on small homogeneous samples, thus caution should be used in the direct extrapolation of these results to large inhomogeneous rock masses having quite different boundary conditions in the earth. The purpose of this supplement is to briefly point out the major effects of these parameters as examined singly, with all others held constant, and to cite some recent results which apply to the main theme on the brittle failure of rocks. The total stress field imposed upon a small volume of porous and permeable rock in the earth's crust may be thought of as the sum of an applied differential stress, plus a lithostatic pressure, plus an interstitial fluid pressure. The differential stress portion may be completely specified by nine components, six shear and three normal. If the small volume element is in rotational equilibrium, by suitably choosing our coordinate axes we may resolve these nine components into the three principal com-

Jan 1, 1967

IN CIRCLES where mining men are wont to fraternize, a statement often heard is: "Yes, I spent six (or two, or ten, or thirty) years down at 'Chuqui.' " This means Chuquicamata, the site in Chile of what in all probability is the world's largest deposit of copper ore. One hears similar remarks regarding Braden and Andes, and, in fact, regarding a score of other big mines in South America, Africa, and elsewhere, but Chuqui seems to lead the others as the locale of engineers who have done a stint in foreign countries. One reason probably is that it is the Anaconda Company's premier foreign operation. Because of its unusual size and the diversity of its operations a great many men are needed. It is a sort of training school for young engineers; but, also, Anaconda has sent down a great many mature members of its big organization for special assignments like metallurgical research or plant construction. Chuquicamata is about 150 miles northeast of Antofagasta, at an elevation of 9,500 ft. It is in an almost rainless desert country where the wind (it is alleged by some) blows most of the time. However, the copper mining entrepreneurs have done their best to make up for what nature has neglected to do in creating a pleasant environment for the people who operate the mines. These include about 160 "foreigners" of whom 86 are from the United States, most of them accompanied by their families. There are 165 Chileans on the staff. Comforts, conveniences, and many luxuries are provided to offset in some measure the disagreeable features of the climate. Nevertheless, as I have implied, engineers at Chuqui generally jump at the chance to become "alumni" when opportunity offers. At the same time, they appear to take pride in their alma mater.

Jan 1, 1957

By H. Yoshida, B. G. Liebmann, R. E. Green

In recent years considerable work has been undertaken in order to gain an understanding of the mechanisms responsible for the generation of recrystal- lization textures in face-centered-cubic metals. Two theories have been proposed, that of oriented growth1 and that of oriented nucleation,' and several attempts have been made to check these theories directly by recrystallizing deformed single crystals.3-5 Two groups, Graham-Cahn and Liebmann-Liicke-Masing, studied the orientation of recrystallized grains and their rate of growth, both using strained aluminum single crystals of commercial purity (Graham et al., 99.6 pct, Liebmann et al., 99.8 pct). Surprisingly, the results obtained by the two groups were completely

Jan 1, 1960

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By A. G. Loomis

IT is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analysis1 of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acids1,2-for example, sodium tannate or gallate-and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shut-downs. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells.

Jan 1, 1940

By A. B. Dyes

In the operation of a water-driven reservoir, a free gas saturation can he established by maintaining production rates fast enough to cause the reservoir pressure to decline below the bubble point. The benefit of such a procedure on the displacement efficiency of the oil by water is illustrated for two types of sandstone samples from one reservoir. Those rock samples showing the poorest recovery to water drive in the absence of a free gas saturation give the most improvement in the presence of a free gas saturation. Employing one type of reservoir fluid (low .shrinkage) the benefit of evolved gas on oil displacement is calculated at several reservoir pressures below the bubble point. This demonstrates the presence of air optimum pressure for water displace,rnent which is .several hundred pounds per .square inch below the bubble point. Displacement of oil at the optimum pressures results in the removal of 7 to I? per cent more oil than would be obtained by displacement at the bubble point pressure. In some instance. this magnitude of increase may be worthy of consideration in establishing the maximum efficient rate of production from many water-driven fields. INTRODUCTION For many years the belief that the use of gas could be combined with that of water to result in a better recovery operation than the use of either of these phases alone has been prevalent in the oil industry. This is evidenced by the several field trials which have employed the injection of gas and water in combination.1.2.v In most cases the small amount of any additional recovery, in combination with the limited knowledge available on the older reservoirs, has left uncertain the influence of gas on recovery in these earlier attempts to combine the use of gas with water. Research studies in recent years have demonstrated through laboratory. floods the magnitude of the benefit of the presence of gas on the displacement of oil from sandstones by water.5,6,7,8,9,10,11 In addition, studies of the distributions of the phases which are present during the displacement process have developed concepts concerning the mechanism by which this benefit is obtained."." It now remains for the engineer to incorporate these findings into the general technology of reservoir operations. It is the purpose of this paper to illustrate that the production of a water-driven reservoir at pressures below the bubble point is one such operation whereby improved oil displacement efficiency can be obtained as a result of gas evolution. The establishment of a gas saturation by evolution of dissolved gas was one of the techniques used by several investigators in the laboratory studies. The possibility of obtaining the benefit of gas evolution in water-driven reservoirs by producing at pressures less than the bubble point has 3150 been pointed out previously." The desirability of this operation has undoubtedly

Jan 1, 1955

By L. E. PORTNER

INCREASING military demands on the petroleum industry have brought into bold relief the crude-oil reserves now available to meet combined military and civilian demands, emphasizing the necessity for a greater efficiency in recovery from what has been discovered than ever before, particularly in light of the absence of new discoveries. This situation-and the fact that the industry, as well as members of the Government charged with governing oil production, desire to meet all crude-oil demands made of the industry with the least loss in tangible reserves through production practices-paves the way for increasing application of sound principles of production engineering and conservation.

Jan 1, 1944

By T. D. Thomas

CONTENTS PAGE T. D. Thomas-Misfires in Anthracite Coal Mines 3 W. H. Forbes-Misfires in Bituminous Coal Mines 12 A. W. Worthington-Misfires in Non-metallic Mining (Limestone) 18 Misfires in Anthracite Coal Mines BY T. D. THOMAS,* LANSFORD, PA. (New York Meeting, February, 1929) IN THIS paper, major attention is given to misfires in mines where electric multiple shot-firing is the system used. Misfires are sometimes caused by one action or condition and at other times by a combination of two or more. They may be divided into two classes: (1) those caused by workers in the mines, (2) mechanical or manufacturer's causes. The second cause will be discussed first. MISFIRES CAUSED BY FAULTY DETONATORS The important part of an electric blasting cap, to the user where multiple shot-firing is done, ass in the steep-pitch, thick-vein, anthracite mines, is the bridge wire. In single shot-firing this factor is not apparent, but in mines where multiple firing is done any variation in the resistance of the bridge wire, where full or even rated battery capacity is required, will most likely cause a misfire The reason for this is obvious. If the resistance in the bridge wires is not the same, some of the detonators will fire because of their greater comparative resistance. Variance in resistance of bridge wires is caused by a slight difference in the diameter of the bridge wire, also to a difference in the composition of the bridge wires. Again, where the bridge wires have become rusted, there will be a variance in resistance. About the year 1922, one of the large coal companies was greatly alarmed by the number of serious and fatal accidents caused by misfires. The general manager issued an order that these accidents must be greatly reduced, and if possible, entirely prevented.

Jan 1, 1929

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller' parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green' dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.' As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

E. A. H. Tays, San Blas, Sinaloa, Mex. (communication to the Secretary*):—The results obtained by Messrs. Hofman and Hayward in their experiments, proving that a low percentage of copper sulphate with a variable percentage of salt, depending on the ore, gives the best results, confirm practical mill-work which I did in 1895. I have none of my notes, taken at the time, to refer to, so have to rely solely on memory, which precludes the conciseness that is alway desirable. In 1894 I took charge of the plant of the San Rafael Company, near Chinipas, Chihuahua, Mex., which at that time was treating a very refractory ore carrying about $15 in gold and from 20 to 25 oz. of silver per ton, the bullion being about 300 fine in gold. The silver in the ore was in the form of a sulphide. Although carrying an average of 0.75 oz. of gold per ton, free gold could rarely be seen by panning, but upon roasting a sample of the ore the gold became visible at once—a result which was discovered by chance and used to advantage later. In order to utilize the old mill to the best advantage, it was decided to use pan-amalgamation after roasting. The roasting, done in a lime-kiln, was similar to the ordinary " burning " operation. The roasted ore was trammed to the mill-bins and crushed by 10 stamps to pass a 30-mesh screen. The pulp was de-watered and fed to four 1-ton pans. My recollection is that upon starting the mill-work, the charge contained 1.5 lb. of copper sulphate and 5 per cent. of salt per ton. From the start the extraction was unsatisfactory and the loss of quicksilver was very large. Experiments were then carried out on a working scale. First, the quantity of copper sulphate was increased 4 oz. at a time; then it was reduced

Jan 1, 1910

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By A. H. Daane, R. L. Myklebust

The yttrium-manganese system has been investigated by thermal, metallographic, and X-ray diffraction methods. There are three intermetallic compounds present: YMn2 which melts congruently, YMn4, which undergoes syntectic decomposition, and YMn,, which undergoes peritectic decomposition. The compound YMn4 is ferromagnetic at room temperature with a Curie temperature of 214°C. There are eutectics at 25.2, 60.9, and 82.0 wt pct Mn which melt at 878°, 1100°, and 1075°C, respectively. Crys-tallographic data are given for YMn4, and YMn12 . The terminal solid solubilities are low. In a general program of study of yttrium metal in this laboratory some alloy systems of this metal with elements of the first transition period have been examined. This work was originally instigated by experiences in cladding yttrium with jackets of some protective metals such as Inconel for high-temperature service in air.&apos; In some cases a low-melting phase was observed to form between the Inconel and the yttrium resulting in failure of the samples. In characterizing this reaction, a survey was made of the systems of yttrium with chromium, manganese, iron and nickel,, and it was found that a eutectic was formed between these metals and yttrium on the yttrium-rich side of the system. This present study of the Y-Mn system was carried out to examine in more detail the alloying nature of yttrium, and to correlate trends that have been observed in previous related studies. It was observed by Voge13 that in the systems of lanthanum, cerium, and praseodymium with each of the metals in the first transition series, the tendency to form compounds diminished in the order nickel, cobalt, and iron while no compounds were formed with manganese, chromium, or titanium. Beaudry and Daane4 observed a similar behavior in the systems of yttrium with some members of the first transition series except that the tendency for compound formation was greater. Both the Y-Ti5 and Y-Cra systems consist of simple eutectics, while in the Y-Fe,7 Y-CO, and Y-Ni4 systems, there are four, eight, and nine compounds, respectively. In addition to the above trends, the similar atomic radii and electronegativities of yttrium and thorium invite a comparison between their alloying behaviors with a common element such as manganese. In crys- tallographic studies, Florio et al.&apos; have identified three intermediate phases in this system which are ThMn2, Th6Mn23, and ThMn,,. Gschneidner and Waber10 have examined published information on alloy systems of the rare-earth metals and have correlated this information with current alloying theory. From their study, they predicted that the Y-Mn system would contain one intermetallic compound. On the basis of this prediction, the trend in the alloying behavior of yttrium with the elements of the first transition series and the alloying behavior of thorium with manganese, one might expect from one to three intermetallic compounds to form in the Y-Mn system. A consideration of Hume-Rothery&apos;s rules of alloying based on size-factor, electronegativity, and valency suggested a small terminal solubility and possible compound formation. The present study was undertaken to confirm these predictions of low terminal solid solubility and compound formation and to establish the general alloying behavior of yttrium with manganese. EXPERIMENTAL Materials. The manganese used in this investigation was obtained from the Foote Mineral Co. as electrolytic plates of 99.9 pct stated purity; the yttrium metal was prepared in this laboratory. Table I gives the analyses of these materials. For the solubility studies at the yttrium-rich end of the alloy system, distilled yttrium, whose major impurity was 200 ppm Ti, was used. Preparation of Alloys. The alloys were formed by comelting the two metals in an are-melting furnace under an atmosphere of argon. The buttons thus formed were inverted and remelted three to five times to promote homogeneity. Due to the high vapor pressure of manganese, it was assumed that the weight lost during are-melting was all manganese. This assumption was based on the very good agreement observed between calculated compositions and chemical analyses of several alloys. The compositions of the dilute alloys used for solid solu-

Jan 1, 1962