Search Documents

By J. W. Onuscheck

The oxygen-fuel oil burner lance is a very useful tool at the Monessen B.O.F. It increases the overall flexibility of the operation. An additional 15,000 to 20,000 ingot tons can be produced at a given hot metal supply. It helps overcome sporadic drops in hot metal thermal values and/or supply. It results in increased yield, in particular, on high carbon heats where much yield was lost on reblow triggered slag reactions. The burner has also been adopted as a standard tool to aid burning in new vessel linings. Overall, steelmaking performance has improved with the use of standard preheat practice. Scrap charges up to 50 percent have been used routinely in times of extreme hot metal shortages, but the performance is weak in some categories. Development of a single step oxy-oil process is in progress. In this process, scrap and hot metal are charged as in the normal B.O.F. practice, but fuel oil is fired with the refining oxygen.

Jan 1, 1972

By E. W. Davis

On the eastern end of the Mesabi Range, in Northern Minnesota, is a large formation of siliceous rock which contains bands and fine grains of magnetite. The magnetite comprises about 35 per cent. of the rock, the remainder being chiefly quartzite and iron silicates. The rock has a specific gravity of 3.4, a hardness of 7, and is extremely tough. This large deposit was located early in the history of the Minnesota iron-ore industry but has not been utilized because of its low percentage of iron as compared with the other Mesabi ores, and because of the difficulty and expense of any milling treatment that would concentrate the iron. An investigation, begun about 3 years ago, shows that the magnetit,e is finely disseminated throughout the entire formation and that there are bands or lenses of higher- and of lower-grade material, in which the magnetite and silicate are intimately mixed. As a result, the scheme of milling adopted must include a fine-crushing plant. As it is necessary to crush to 200 mesh in order to produce the desired grade of product, the fine crushing is one of the largest items of expense and for this reason has been given detailed study. It is the purpose of this paper to present some of the results of the work on fine crushing, as to both theory and practice. Previous to fine crushing the part of the rock that contains little or no magnetite can be discarded by magnetic concentrators after each reduction in size in the dry-crushing plant. This-makes it possible to fine-crush a minimum of rock and also establishes the feed to the ball-mill as below % in. The fine-crushing problem, then, consists simply in crushing the rock from 1/4 in. to 200 mesh at the minimum expense. Equipment of the Testing Plant In order to determine, among other things, the operating conditions of the ball-mill when working on this rock, a test mill of about 300 T. daily capacity was erected at Duluth, Minn. The fine-crushing plant contains a Hardinge 8-ft. by 22-in. (2.4-m. by 55.8-cm.) conical mill, a 6- by 27-ft. (1.8 by 8.2-m.) Dorr duplex bowl-type classifier, a 41/2-ft. (1.37-m.) standard Akins classifier, and the auxiliary machinery necessary to handle the products. Each machine is driven by an individual motor, each of which is provided with meters for measuring the power required. Over 150 tests have been made in the ball-mill, varying in

Jan 1, 1920

By Arthur Hockman, Howard W. Jaffe, Howard F. Carl

THE problem of establishing practical techniques for evaluating natural corundum ores arose from the desire to improve the existing purchase specifications for crystal corundum procured by the Federal Government for stockpiling. Such purchase specifications had been developed for a large number of products, including minerals and ores considered to be critical and strategic because of the country's dependence on foreign sources of supply. It will be apparent to anyone considering the subject of purchase specifications that the determination of whether or not a submittal meets the specifications is a prime consideration. Consequently satisfactory specifications for minerals should not only incorporate physical, chemical, and mineralogical requirements that are practical but should also establish the means by which both buyer and seller can be assured that materials meet stated requirements. The Munition Board's Material Purchase Specification for corundum, dated February 1954, covered two grades of crystal corundum intended primarily for abrasive use. It established limits of size and of composition: Grade A, at least 95 pct +3 mesh and 92 pct alumina (Al2O3); Grade B, at least 95 pct +7 mesh and 90 pct alumina. It also specified that "of each lot of material, not less than 95 percent shall have a hardness equal to or exceeding nine (9) on Moh's Scale." These specifications were unsatisfactory for several reasons. They did not allow the purchase of lower grades of corundum being used by industry. Neither did they specify exactly what a corundum ore actually was, except that it should contain so much alumina and have a certain scratch hardness. Nothing was said about the abrasive qualities of the material that was to be purchased primarily for abrasive use. During the period 1946 to 1948 supplies of the two grades defined in the then current specifications continued to decrease. Early in 1949 industry recommended that the finer sizes of corundum known as "crystal corundum concentrates," ¼-in. to 16-mesh material, be added to the stockpile specifications and that lower grades of crystal corundum also be included. In the spring of 1949 the National Bureau of Standards and the Bureau of Mines were asked by the Munitions Board to cooperate in developing more practical specifications for grading natural corundum ores. The National Bureau of Standards indicated that it would investigate physical test methods for determining abrasive characteristics of corundum, and the Eastern Experiment Station of the Bureau of Mines at College Park, Md., stated that it would consider the mineralogical aspects of the problem. Members of these two agencies, in consultation with representatives of the Office of Materials Resources of the Munitions Board and of the Federal Supply Service of the General Services Administration, and with the cooperation of industrial suppliers and consumers of abrasive corundum, developed, in a fairly short time, more practical specifications for six grades of corundum ores. The new specifications, issued January 1951, were for corundum, natural crystals, as by this time high-purity synthetic corundum was available and widely used. Nevertheless, for certain specific applications the natural product was preferred over the synthetic material. It has been extensively used in forming snagging wheels. It breaks into more or less cubical particles, whereas artificial corundum fractures into splintery shapes. These produce irregular cuts in glass, while the more symmetrical shape produces a more uniform ground surface. For this reason natural corundum has been preferred for certain types of lens grinding. Pure corundum is clear, colorless alpha alumina (A12O3), but it is rarely found in nature in this form. The most important gem varieties include the blue and yellow sapphires and the ruby. Minute impurities of titanic oxide impart a blue color,

Jan 1, 1955

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By M. B. Bever, A. K. Jena

THE heats of formation ?H at 273°K of the compound AgMg as a function of composition have been measured by solution calorimetry.1 The value at the stoichiometric composition is -4.41 kcal per g-atom. From electromotive force measurements2'3 the heat of formation at 773°K of stoichiometric AgMg has been determined as -5.19 kcal per g-atom.4 The combination of these two values results in an unusually high negative temperature coefficient of the heat of formation d?H/dT = ?Cp = -1.6 cal per g-atom-OK. By contrast, published heat contents of the compound AgMg and the component elements above room temperature5 indicate that the temperature coefficient of the heat of formation of AgMg is nearly zero. In this communication calorimetrically measured heats of formation of A.K.JENA,Junior- MemberAIME,andM.B. BEVER,Member AIME, are Staff Member, Division of Sponsored Research, and Professor of Metallurgy, respectively, Massachusetts Institute of Technology, Cambridge, Mass. Manuscript submitted July 1, 1968. IMD AgMg below room temperature are reported and the temperature dependence of the heat of formation is discussed. The heat effects of additions of samples of the compound AgMg containing 50.1 at. pct Mg to liquid tin-rich solutions at 623°K were measured in a solution Calorimeter.6 The heat effects of additions plotted against the average of the atom fractions of solutes in the solution before and after each addition were a linear function of composition from which the heat effect at infinite dilution was obtained, Table I. The calorimeter was calibrated by additions of tin; the heat content (H623°K - H273°K) of tin was taken as 4.08 kcal per g-atom.4 The heat effect at infinite dilution of an addition of where heat of formation of AgMg at T°K, T = temperature from which samples are added (78°, 195°. and 273°K), Xi = atom fraction of i in AgMg, ?Hi = relative partial gram-atomic enthalpy of i in tin-rich solution.

Jan 1, 1969

By Frank Foote, Eric R. Jette

In a recent article,1 the authors reported the results of an X-ray investigation on the range of solid solutions that occurs in the iron-oxygen system in the vicinity of the compound FeO, which frequently is called "wüstite." The object of that investigation was primarily to study the unusual type of solid solution phenomena involved in this range. Briefly summarized the results were: 1. The NaCl type of lattice found by earlier workers was confirmed. 2. The lattice dimensions decrease rapidly with decrease in iron content. 3. No alloy that was a homogeneous single phase was ever found at compositions beyond 76.80 per cent Fe, while the theoretical iron content of FeO is 77.73 per cent Fe. 4. Measurements of the densities and lattice constants led to the conclusion that the form of substitution was complex, an FeO group being replaced by oxygen. Such a substitution, of course, is equivalent to removing an iron atom (or ion). The ideal unit cell of FeO can be considered as containing four groups of FeO and, thus, when this type of substitution takes place, there remain in the unit cell three FeO groups and an oxygen, or a total of seven atoms with a gross formula of Fe3O4 instead of the original Fe4O4. 5. This was the only interpretation that would fit the experimental results and at the same time be consistent with (a) the previously determined fact that the FeO lattice is ionic (i, e., consists of Fe++ and O? ions) and (b) the chemical fact that as the oxygen content of the substance increases, ferrous iron becomes oxidized to ferric iron. The experimental results of this investigation are included in Fig. 1. The purpose of the present investigation was to determine the limits of this homogeneity range by means of the X-ray structure analysis. This method has been applied frequently to the study of solid solutions by Westgren and his coworkers as well as by other investigators. The principle is simple: if the change in lattice constant with composition is

Jan 1, 1933

By C. M. Fellman

AVAILABLE data for the first nine months of the Year indicate that accident occurrence in metal mining was well on its way to an all-time low for 1939. However, the relatively rapid pickup in mining production in the fall will be likely to boost both accident occurrence and also accident rates. Results of the National Safety Competition for 1938, the fourteenth of its kind conducted by the U. S. Bureau of Mines, were published in August, 1939. W. W. Adams, statistician of the bureau, states that "with 345 mines and quarries competing, more than in any previous year except 1931, the contest revealed low accident rates at many of the enrolled plants and, which is even more remarkable, it revealed 113 mines and quarries at which no lost- time accidents occurred during the con- test year." The National Safety Competition provides a means whereby mines and quarries may engage in active competition to stimulate their safety programs. Companies in the contest can compare their records with those of similar plants operating elsewhere and thereby determine to what extent their safety programs are successful. The Joseph A. Holmes Safety Association gave over 150 awards for safety performance in the mineral industries in 1939 and a remarkable phase of these awards was the considerable number given to individual miners who had worked fifty or more years without sustaining a lost-time accident.

Jan 1, 1940

By T. Prof. Egleston

How to interpret the composition of rocks has been a question which has caused a great deal of discussion and investigation among geologists and chemists. It is evident that that analysis will give the clearest results, which will give the relative proportion of the different minerals composing the rock as well as the weight of their different constituents. This, however, is a very difficult matter, and in those rocks which seem to the naked eye entirely compact, like obsidian and other rocks of that class, appears to be impossible. Cordier, in the early part of the century, invented a process which is known as the " mechanical analysis of rocks," which is really a method of mechanical preparation, and consists in crushing the rock to a certain fineness, and then, by virtue of their density, washing out the different minerals, so as to make a mineralogical analysis, separating completely the different constituents of the rocks. In the hands of so skilful a man, this was a comparatively easy matter, and Cordier found no difficulty in ascertaining the mineralogical composition of a rock. The ultimate chemical composition was ascertained from the sum of the elements contained in the different materials. In the light of to-day, it is very easy to see that the complete chemical analysis of the rock does not necessarily lead to the explanation of its character. It has been so difficult, however, to have any other kind of analysis made that most chemical examinations have been made as ultimate, and not as mineralogical analyses. The panning out of the different minerals composing the rock, which are often very nearly of the same specific gravity, is so difficult that a person of ordinary mechanical skill is scarcely able to do it; consequently the mechanical analysis which Cordier proposed, and was able himself so skilfully to effect, has never been practiced to any extent. A school was formed in France consisting of a very small number of Cordier's followers, which, in face of the difficulty of acquiring the method, very soon died out as a school, though some of his most skilful followers are still living. The next important step in ascertaining their composition was to out the rock into transparent sections and examine the minerals with

Jan 1, 1875

By H. A. J. Wilkens, H. B. C. Nitze

At the Atlanta meeting of the Institute in October,' 1895, some brief remarks were made by Mr. Wilkens on the above subject. It is the object of this paper to set forth the substance of these previous statements, embodying therewith additional information gained since that time, and a brief illustrated description of the method and means of the separation.* Lack of time will unfortunately not allow as complete a resume of the subject in all its phases, especially those relating to the scientific side of the question, as its novelty and importance would warrant, so that even this paper must be considered a preliminary one. It is hoped that at some future meeting of the Institute we may find an opportunity of presenting supplementary data of interest. The paradoxical title above used requires some explanation. The term " non-magnetic material " is applied to such substances as have heretofore been considered non-magnetic in the arts, more especially in the practice of ore-concentration. Scientifically, it has been shown by Faraday, Plucker, Wiedemann and other physicists that magnetism is an inherent property common to all substances, solid, liquid and gaseous, i.e., all suhstances are either attracted or repelled by the poles of a magnet, although ill the great majority of cases the manifestation of this

Jan 1, 1897

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

By H. L. Sauder, J. L. Newman, C. Waddell

An instrument capable of measuring subsurface flow rates is described. The instrument is self-contained and may be run on piano wire line. It detects flow by means of an impeller suspended between two torsion wires. The force of the well fluid striking the impeller causes the impeller to rotate, exerting a torsional force to the wires. This force is determined by recording the angle of rotation of the impeller on film using a battery-driven, clock-controlled camera. The impeller is sensitive to flow in either direction and the same instrument can be used to measure injection as well as production rates. Changes in direction of flow, such as might be caused by thief zones, are measurable and are indicated by a reversal of the direction of rotation of the impeller. Adjustment of the sensitivity of the instrument to measure a wide range of flow rates is accomplished by the use of different size torsion wires. An umbrella-type fluid trap, which contacts the casing or wellbore, diverts the flow through the flow tube. The fluid trap remains closed while rurrning in the hole and can be opened at any point in the well. The instrument with the trap closed is 1 3/4 in. OD and may be run through 2 in. tubing. Successful flow profiles have been made on wells with flow rates ranging from 60 BID to 4,000 B/D at surface pressure up to 4,500 psi. The instrument is designed for high-pressure and high-temperature operations. INTRODUCTION The need for an instrument that will measure flow rates in a wellbore is as old as reservoir engineering itself. A number of such devices have been designed within the past few years. Some of these have been described in the literature1,2,3,4,5,6 One of these devices1. a hot-wire anemometer type, made many successful jobs in dry gas producing areas. Difficulty was encountered when this flowmeter was used in wells producing liquids and development work was initiated to overcome this difficulty. The present flowmeter is the result of this work and provides an instrument with a wider range of application in the industry. Consider- able development work has been done on the tool involving many changes in the mechanics of recording the flow readings, however, the basic principle of flow detection has remained the same since its inception. PRINCIPLE OF OPERATION The basic principle of operation of the flowmeter is the utilization of a portion of the kinetic energy of flowing well fluid to impart a rotational force to an impeller suspended between two torsion wires. This impeller, Fig. 1, is a screw-type propeller with the blades having a pitch angle of 40. As the well fluid passes through the instrument it strikes the impeller. The resulting force rotates the impeller and twist\ the torsion wires to a balance point at which the torque imparted to the wires balances the force required for the impeller to deflect the well fluid. The impeller is symmetrical and a change in direction of the flow results in a reversal of the direction in which the impeller is deflected. Thus the direction of the flow as well as its velocity is indicated. A dial is attached to the impeller by means of a hollow tube through which the upper torsion wire extends. The angular position of the impeller is recorded by photographing the dial at frequent intervals. In any given set of torsion wires the modulus of shear and polar moment of inertia remain constant and the deflection varies directly with the applied torque. The deflection imparted to the torsion wires also varies as the square of the fluid velocity. Further, the velocities represented by any two given deflections hear the following relationships: and Where V = velocity of flow stream and O ;= deflection. This is the basic relationship which is used to calculate the relative velocities represented by a given set of deflections where the velocity represented by any one of the deflection readings is a known quantity. For a given torque, the deflection of the torsion wire varies inversely as the fourth power of the wire diameter. Wire sizes ranging from ,005 in. in diameter to .022 in. in diameter can be used. The range of

Jan 1, 1957

By D. E. Thomas, C. E. Birchenall

ALTHOUGH Eoltzmann gave a mathematical solution for the diffusion equation (for planar diffusion in infinite 01. semi-infinite systems only) in 1894 allowing for variation of the diffusion coefficient with a change in concentration, it was not until 1933 that this solution was applied to an experimentally investigated metallic system. The calculation was carried out by Matano' on the data obtained by Grube and Jedele3 for the Cu-Ni system. Since that time concentration dependence of the diffusion coefficient has been demonstrated for many pairs of metals. However, the nature of this dependence has never been fully elucidated. Many investigators have suspected that these variations could be related to the thermodynamic properties of the solutions, one of the earliest explicit statements being contained in a discussion of irreversible transport processes by Onsager' in 1931. Development along these lines has been greatly retarded by the lack of reliable data on the variation of tliffusivity with concentration, the paucity of the thermodynamic data for the same systems at the same temperatures and compositions, and an incomplete understanding of the relation of the thermodynamic properties of the activated state for diffusion to the bulk thermodynamic properties. The last factor has been discussed by Fisher, Hollomon, and Turnbull.5 In many instances where data exist, it is difficult to know which are acceptable. This problem probably applies more strongly to diffusion data than to activity measurements. For instance, four sets of observers"-" have reported self-diffusion coefficients for copper. The average spread between extreme results is a factor of about four, though the individual sets of data are self-consistent to about 20 pct. Thus one or more factors are out of control, at least in these experiments, making estimates of internal error unreliable. The most reliable diffusion data in most systems have resulted from the use of welded couples with a plane interface from which layers for analysis are machined parallel to the interface after diffusion. The layers are analyzed, and the result is a graphical relation between distance and concentration, usually called the penetration curve. Given the same set of analytical data and distances and following the same procedure in computation, different observers will generally produce diffusion coefficients which vary appreciably, especially at the extremes of the concentration range. Experiments must be carefully designed so that the precision is good enough to answer a particular question unequivocally. In the first calculation of the dependence of the diffusion coefficient on concentration in the metallic solid solution Cu-Ni, Matano found that the coefficient was insensitive to concentration from 0 to 70 pct Cu, after which it rose more and more steeply to some undetermined value as pure copper was approached.' The same behavior was reported for Au-Ni, Au-Pd, and Au-Pt.* The data used were those of Grube and Jedele which were very good at the time, but are not considered particularly good by present standards. Furthermore, the method of calculation makes the ends of the diffusion coefficient-concentration curve unreliable. For better reliability, the high copper end of the curve has been checked by incremental couples, where the concentration spread is 67.7 to 100 atomic pct Cu. The implication of the curves calculated by Matano was that diffusion is very concentration sensitive in one dilute range of this completely isomorphous system and hardly at all in the other. Matano's result is confirmed. Later Wells and Mehll0 published data on diffusion in Fe-Ni at 1300°C, which represent a thorough test of the shape of the concentration dependence curve. They ran couples with the following ranges of nickel concentration: 0-25 pct, 1.9-20.1 pct, 0-20.1 pct, 20.1-41.8 pct, 0-99.4 pct, and 79.3-99.4 pct. Although the trend of the data indicates an S-shaped concentration dependence, their curve was drawn to the pattern set by Matano. Their original data have been recalculated for the 0-99.4 and 79.3-99.4 pct couples. Wells and Mehl's points and two independent recalculations from the raw data are plotted in Fig. 1. What appears to be the best curve is drawn through them. This curve shows little sensitivity to composition in both dilute ranges with a strong dependence at intermediate composi-tions.? Similar experiments on the Cu-Pd system are reported here at temperatures where solubility is unlimited. These lead to the same type of concentration dependence for the diffusion coefficients as was found upon recalculation of the data for the Fe-Ni system. Experimental Procedure Cu-Pd: The concentration dependence of the diffusion coefficient may be determined by the use of

Jan 1, 1953

By Dr. T

THE application of electricity in the extraction of metals has hithcrto been chiefly confined to the electrolysis of dissolved or fused compounds of these by varios methods. The power of electric currents to generate intense heat in their passage through a resisting medium has, however, long been known, and the late W. Siemens thereby succeeded in fusing considerable quantities of steel. But it was reserved to Messrs. Eugene 11. and Alfred H. CoWles, of Cleveland, Ohio, to take a new step in the metallurgic art by maKing the heat thus produced a means of reducing in the presence of carbon the oxides not only of the alkaline metals, but of calcium, magnesium, manganese, aluminium, silicon, and boron, with an ease that permits the production of these elements and their alloys with copper and other metals 011 a commercial scale. In the apparatus devised and now employed by the Messrs. Cowles, a column of fragments of well-calcined charcoal, so prepared and arranged as to present the requisite electrical resistance, is imbedded horizontally in finely pulverized charcoal, and covered by a layer of the same material coarsely broken, the whole being arranged in a box of fire-brick, covered with perforated tiles and opened at the ends to admit two carbon electrodes an inch and a half in diameter.

Jan 1, 1886

By N. Marusov, D. K. Lowe, J. C. Karp

This paper considers, from an engineering viewpoint, several factors involved in creating, designing and locating horizontal barriers for controlling water coning. This is an effort to consolidate new concepts with previous information so that a reasonable selection of barrier materials, dimensions and vertical position can be made. Coning theories previously developed are briefly reviewed and an effort i,s made to reduce the results of coning-theory calculations to a point where routine calculations can be made with a desk calculator. It is expected that these simplified calculations will give usable predictions of the amounts of improvement attainable with barriers of various dimensions. Apparatus and procedures used for testing the suitability of commercial cements are described and test results are presented. INTRODUCTION Just about as soon as the phenomenon of water coning was recognized as an oilfield problem, there were suggestions that the production of water coning could be controlled or completely suppressed by means of horizontal barriers. It was also suggested that natural barriers such as shale streaks were helpful in restricting bottom-water production. The implication was that wells not having the benefit of continuous shale streaks to suppress bottom waters should, in some way, be supplied with an artificial barrier. With regard to the selection of barrier materials, there are many references which give the merits of liquid barriers.',' These liquids include surface-active agents," recipitates' and emu1sions. There is no real need to review the merits of these materials again. This paper deals with the use of solid barriers which could be made from various cements. The two major restrictions placed on these barrier cements are that (1) they must be commercially available in large quantities, and (2) they must be applicable by means of standard tools and equipment with techniques that have been fully developed and are in general use at the present time. A schematic drawing of a horizontal barrier in a reservoir is shown in Fig. 1. Two maximum stable water cones are illustrated-—-one for the wellbore diameter and the other for a barrier. A maximum stable cone is one that has attained its maximum volume at the critical production rate and is on the threshold of producing water. The volume displaced by each water cone and the rise in water table are indications of the amount of water-free oil produced. Corrections for porosity, connate water and residual oil, of course, must be applied. The water-oil interface which defines a maximum stable cone is called a free surface. It is a surface over which the pressure is constant. This free surface has the shape of a limiting streamline at and below which there is no movement or transport. The shape of the water cone describes the pressure drop in the reservoir. The effect of a completely impermeable barrier on the cone shape is essentially the same as extending the wellbore out to the barrier radius. The placement of a horizontal barrier requires that a horizontal fracture be created using a single-point entry technique. Two methods may be employed for filling this fracture. One method consists of propping the fracture before filling with cement. The other consists of fracturing with fracture fluid, then immediately following with cement

By J. T. Burwell, J. Wulff

As is well known, the alloys of iron containing 18 ± per cent chromium, 8* per cent nickel and less than 1.2 per cent carbon exhibit the same allotropic modifications as iron. The face-centered cubic or gamma phase is stable at high temperatures and the body-centered cubic or alpha ferrite is presumably stable at room temperature. The transformation from the gamma phase to the alpha phase in alloys of the above composition (18-8 or stainless steel) is sluggish; even moderately rapid cooling permits the retention of the gamma phase. Cold-work, however, causes the transformation from gamma to alpha to occur at room temperatures. It is difficult, nevertheless, to induce complete transformation regardless of the method of cold-working. Since metallographic polishing is very effective in transforming the surface austenite to ferrite, as indicated by the magnetic studies of Buehl and Wulff,1 it was decided to investigate the phenomenon by electron diffraction methods. Apparatus The apparatus used (Fig. 1) was a hot-filament type employing movable slits, similar to that described by Germer.2 The sample-to-photographic plate distance was 69 cm. and the accelerating voltage 30 kv. Since electrons do not in general follow geometrical paths, it is necessary that either the electron source or the sample be movable in a plane normal to the beam. In this case the sample is fixed and the electron source is movable. The source is adjusted until the shadow of the sample appears in the brightest part of the beam as viewed on the fluorescent screen, then the slits composing the two pinholes are inoved into position one by one. The system is evacuated by means of a mercury diffusion pump backed up with a Cenco Hypervac oil pump. Pressures lower than 10- mm. of Hg are read on a calibrated ionization gauge.

Jan 1, 1939

By J. T. Burwell, J. Wulff

As is well known, the alloys of iron containing 18 ± per cent chromium, 8* per cent nickel and less than 1.2 per cent carbon exhibit the same allotropic modifications as iron. The face-centered cubic or gamma phase is stable at high temperatures and the body-centered cubic or alpha ferrite is presumably stable at room temperature. The transformation from the gamma phase to the alpha phase in alloys of the above composition (18-8 or stainless steel) is sluggish; even moderately rapid cooling permits the retention of the gamma phase. Cold-work, however, causes the transformation from gamma to alpha to occur at room temperatures. It is difficult, nevertheless, to induce complete transformation regardless of the method of cold-working. Since metallographic polishing is very effective in transforming the surface austenite to ferrite, as indicated by the magnetic studies of Buehl and Wulff,1 it was decided to investigate the phenomenon by electron diffraction methods. Apparatus The apparatus used (Fig. 1) was a hot-filament type employing movable slits, similar to that described by Germer.2 The sample-to-photographic plate distance was 69 cm. and the accelerating voltage 30 kv. Since electrons do not in general follow geometrical paths, it is necessary that either the electron source or the sample be movable in a plane normal to the beam. In this case the sample is fixed and the electron source is movable. The source is adjusted until the shadow of the sample appears in the brightest part of the beam as viewed on the fluorescent screen, then the slits composing the two pinholes are inoved into position one by one. The system is evacuated by means of a mercury diffusion pump backed up with a Cenco Hypervac oil pump. Pressures lower than 10- mm. of Hg are read on a calibrated ionization gauge.

Jan 1, 1939

By N. A. DeCecco, H. M. Meyer

IN the early stages of a titanium brazing investigation, binary titanium systems partially or completely known and fundamental metallurgical data were surveyed to select the pure metal most likely to be satisfactory for producing a ductile high strength joint. The phase diagrams for the purpose of this survey were classified into two groups: 1—systems with large solubility in ß titanium, but negligible solubility in a titanium, and 2—systems with large solubility in a titanium. Those metals with melting points believed to be too high or too low for titanium brazing (Tim = 1730°C) were eliminated from consideration. The melting points of vanadium, tungsten, tantalum, hafnium, zirconium, and the platinum group are too high and those of zinc, lead, cadmium, and tin are too low. The remaining metals were grouped as follows: 1—large ß solubility: Cr,¹ Mn,² Fe;³ CO,4 Ni,5 Cu,6 Be,' Si." —large a solubility: Al.9

Jan 1, 1954

By W. R. Foster, J. M. McMillen, A. S. Odeh

The complete equations of average linear momentum balance for a single-phase fluid in an incompreisible, homogeneous, porous medium are derived. The derivation begins with Euler's equation of motion for a continuum and uses an integral transform recently developed by Slattery. 7 For steady flow of a compressible, Newtonian fluid, the usual equations of motion result. For transient flow, the space-time description of the pressure is determined in the lowest approximation by the telegrapher's equation. From the analysis a new phenomenological coefficient results which connects the viscous traction to the deriv ative of the linear momentum density. The magnitude of this coefficient determines the velocity of sound through the pore structure in this approximation to the pressure field. INTRODUCTION The modification of Darcy's law of momentum balance for steady, single-phase flow through porous media has been discussed for many years. The first modification was suggested by Forcheimerl who added terms of higher order in the velocity. These can be expected to appear because the underlying microscopic equations of momentum balance are themselves nonlinear in the point velocity field. The Reynolds tensor pvv, which represents the convective flux of momentum density, appears in the momentum balance equation. Only in rectilinear flow (parallel stream lines) does the divergence of this tensor vanish. Since the steady flow stream lines in most porous media are not parallel, nonlinear dependence of the pressure gradient on the velocity should naturally appear. This nonlinearity has nothing to do with turbulence in the ordinary sense of random fluctuations in the pressure and velocity fields. It arises simply because the stream lines converge and diverge, even for steady flows. Klinkenberg2 demonstrated that the permeability coefficient in Darcy's law depends on the absolute pressure or, alternatively, on the density field. However, because he neglected inertial terms of the Forcheimer type, his correction coefficient could not be represented by a constant but tended toward a constant as the velocity decreased. Forcheimer's and Klinkenberg's modifications can be combined in a rigorous way to account for both inertia and slip during steady flow. This will be shown in a future paper. The transient change of pressure in porous media has been described by the diffusion equation.3 This form results from eliminating the velocity and density fields from a combination of the equations of motion in the form of Darcy's law, the continuity equation and an equation of state. Fatt4 suggested that the cause of deviations from the prediction of the diffusion equation for pressure transients lies not in the choice of Darcy's law as the equation of motion but on the existence of dead-end pores which might invalidate the averaged equation of continuity. On the other hand, Oroveanu and Pascal5 noted chat the time derivative of the momentum density must be included in the equations of motion since this measures the local rate of change of momentum density. Their differential equation for pressure is the telegrapher's equation (neglecting gravity). However, their form of this equation predicts that the speed of pressure propagation through the pore structure is the same as that through the bulk fluid. M. K. Hubbert6 attempted a derivation of Darcy's law by volume averaging the Navier-Stokes equations. Since these equations represent momentum balance at a point within an open set of points containing the fluid itself, Hubbert's volume averaging cannot lead to tenns involving transfer of momentum between the fluid and the walls of the pores. Once these viscous tractions are lost by choosing a control volume containing only fluid, they cannot

By H. C. Miller

The energy stored in the compressed natural gas absorbed in or otherwise associated with the oil in reservoir sands is usually the most important factor in oil recovery. It is recognized that hydrostatic pressure and gravity may aid materially in the drainage of oil, but in the early life of the majority of fields the principal source of propulsive energy is the expansive force of the gas associated with the oil. Since gas is admittedly the most important factor in the production of oil, its control so as to produce the maximum amount of oil with the minimum amount of gas will be reflected in increased oil recovery from reservoir sands. Controlling the gas means regulating its expansion so that the velocity of flow of oil through the channels in the reservoir sands is neither so great that frictional resistance becomes excessive nor so slow that the gas, because it can travel more rapidly than oil through the irregular passageways in the sands, will by-pass and reach the well without. doing useful work in bringing oil from the sands. Oil and gas flow from the reservoir sands to the well because of differences in pressure. The rate of flow is dependent upon the differential pressures existing in the sands and in the well. By altering the amount of back-pressure maintained on the well this differential pressure can be regulated and changed from a maximum (well flowing "wide open") to a minimum when there will be no flow. Oil and gas flow through the irregular channels in reservoir sands at different rates mainly because of the fact that one is a liquid and the other a gas. Therefore, because oil and gas have different characteristics of flow, application of back-pressure, changes the rates of flow with relation to one another so that wide variations in gas-oil ratios are possible. Obviously, the formation gas energy will be utilized most efficiently when a unit of gas delivers the maximum amount of oil to the well. Determination of Necessary Back-pressure The amount of back-pressure that should be maintained against the producing sand in order that the minimum amount of gas will be produced with each barrel of oil can be determined only by actual field tests made

Jan 1, 1929

By Victor O. Homerberg, Dexter N. Shaw

A study of the correlation of the mechanical properties and of the microstructure with the heat treatment of 60-40 brass has been confined, heretofore, to the rolled or extruded material as received from the mannfacturer. The results obtained by Babson and Buhler,' Bengough and Hudson12 Stead and Stedman,3 and Brayton4 have been confined to the treatment of the material as received. No attempt was made to get the material into a given condition and then to work from this basis. To start with a given structure would have the decided advantage of making the work independent of the original condition, hence, to make the results reproduceable. In a previous paper, it was shown, in connection with the study of the transformation that occurs at about 470" C., that if specimens were quenched to produce the beta structure and then reheated, the beta would begin to break down, at approximately 200" C., into a very finely divided alpha. It was predicted that important results might be obtained if test pieces were to be given a similar double heat treatment and then tested for the mechanical properties as well as a study of the microstructure. The material used in the present investigation was a 3/4-in. round bar of extruded muntz metal of the following composition: Copper, 61.05 per cent.; zinc (by difference), 38.90 per cent.; lead, 0.05 per cent.; iron, trace; tin, nil.

Jan 1, 1924