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

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

Jan 1, 1949

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,' and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.' Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By A. H. Willis

In this paper the results of an exploratory study conducted by personnel of the Knolls Atomic Power Laboratory on 18.6, 22, and 40 wt pct uranium-zirconium alloy will be presented. LARGE power output and long life or endurance from small, compact nuclear reactors require the use of enriched uranium for a fuel material. However, the ability to remove heat from the element, the tolerable fission product concentration, or some physical limitation of the system can limit the allowable fuel enrichment, or the volume of the fuel. In such an event, the fuel-element designer must find a suitable diluent for the uranium. Zirconium is an attractive material for such a purpose as it has good nuclear properties and a low absorption cross section. Because it has a good corrosion resistance in water, zirconium is a suitable cladding and the uranium-zirconium alloy makes a good core material. The alloy has a high thermal conductivity, a low elastic modulus, and a low thermal-expansion coefficient, all of which tend to minimize the thermal stresses in the core. Furthermore, the unirradiated material is reasonably ductile and has adequate strength. DESCRIPTION OF SAMPLES Two types of cylindrical samples were used in this study 1) short, 1/2-to 1-in.-long samples to test the irradiation stability of the alloy and 2) 2-ft-long samples to investigate the resistance of an element to longitudinal deformation. Composite samples having 0.060-to 0.140-in. core diameters and clad with a 0.010-in. thick zirconium jacket were fabricated by coextrusion and by hydrostatic pressure bonding of the cladding to the preformed core material. Both fabrication processes produced the uniform metallurgical core-to-cladding bond which was felt necessary to minimize the uncertainty of the central core temperature. Both consumable-arc and induction-melting techniques were used to melt the uranium-sponge zirconium core alloy. Since a graphite crucible was used in induction-melting this alloy contained more carbon impurity, which resulted in a finer grain size than the arc-melted alloy. The core to cladding interface was uniform in elements coextruded from the fine-grain, induction-melted core material, while those elements fabricated using arc-melted core material had very irregular interfaces because of the coarser grain size. Both cold-worked and heat-treated fuel materials were irradiation tested. Cold-worked alloys were swaged to about a 5 pct final reduction in area without subsequent annealing. The heat-treated alloys were heated to 800°C, held at temperature for 15 min and furnace-cooled to about room temperature. This

Jan 1, 1960

By Rex B. McLellan

Studies of the eyuilibrzum between ferrite and austenite with gas mixtures (CO + CO2 and H2 + CHe) have been used as a means of deducing the energy and vibrational entropy of carbon atoms in dilute interstitial Fe-C solutions. A simple model for dilute interstitial solutions is given which enables a solubility equation for the equilibrium between the gas mixtures and the solid to be deduced. This solubility equation is used to estimate the partial In this work measurements of the equilibrium between dilute solid solutions of carbon in iron and gaseous mixtures of CO2 + CO and CH4 + Hp have been analyzed using theoretical solubility equations deduced from a knowledge of the thermodynamic parameters of the gas mixtures and an appropriate model for the solid solution. The solubility equations are deduced by equating the chemical potential of carbon atoms in the gas thermodynamic functions of dilute Fe-C solutions from the measured equilibrium between the solid and the gas mixtures. It is shown that the vibra-tional entropy of a carbon atom in a and y iron is smaller than the corresponding entropy 01. a nitrogen atom in solid solution inferrite or austenite and that there is little difference between the vibrational entropies of both nitrogen and carbon atoms in ferrite and austenite. and solid phases. The chemical potential of carbon in the gas is found from a simple statistical mechanical analysis of the gas mixtures utilizing spec-troscopic data while that for carbon in the interstitial solution is found from a model in which the carbon atoms act as bound oscillators distributed in a random fashion in the solution. The solid solution is dilute enough to enable solute-solute interactions to be ignored. Thus the configurational entropy of the solution is ideal but the mixing entropy contains additional excess terms due mainly to the vibrational changes occurring on solution formation. The partial excess entropies (and the partial energies) do

Jan 1, 1965

By J. L. Lytton, T. E. Tietz

The recovery of flour stress of recrylstallized are-cast molyhdenum after 10 pet prestrain at 150°C was studied for recovery temperatures of 725o 801o and 901oC. The yield phenomenon observed after recovery was such that the yield drop diminished and disappeared as recovery proceeded. A fractional flow-stress recovery parameter fr, was developed and it was shown that, independent of recovery ternperatzwe, equal f, values of about 0.16 produced superposition of stress-strain curves except for the initial yield phenomenon. The activation energy for low degrees oj recovery was found to he 32,600 cal per mole, in close agreement with a reported valzie for difjzdsion of carbon in molybdenum. For values of fr greater than about 0.15 where recovery was thought to predominate over strain aging, the activation energy varied from 43,600 to 82,500 cal per mole and increased with increasing recovery and recovery temperature. A 10 pet pre-strain shifted the ductile-brittle transition temperature, as indicated by tensile elongation, from 10°C. to about -22"C. A 100-hr recovery anneal at 801oC was shown to shift the transition temperature to about —5oC, the major shift occurring during the first hour of recovery. ThE recovery of cold-worked metals is accompanied by changes in the arrangement of the dislocations generated during cold work. In recent years, the use of transmission electron microscopy has allowed direct observation of some of the dislocation configurations formed, such as "tangles", networks, cells, subboundaries, and loops. These observations have recently been reviewed by Keh and Weissmann.' Accordingly, some understanding has been gained concerning the nature of the dislocation rearrangements involved. The relationship between recovery and the decrease of mechanical strength, however, has only recently been explored. Previous efforts of the authors were directed toward investigating the decrease of tensile flow stress of aluminum and Al-1 pet Mg during recovery2 and the effects of concurrent elastic and plastic strain on the flow-stress recovery of aluminum.3 In addition, an investigation of the effect of four different solute additions on the tensile flow-stress recovery of aluminum has been made.4 Many important metals, however, have the bee crystal structure, e.g., iron, molybdenum, tungsten, vanadium, columbium, tantalum, and chromium. These metals might be expected to behave differently during recovery from those with other crystal structures for two reasons. First, the previous and present investigations of aluminum and its alloys have shown that tensile flow-stress recovery is strongly affected by foreign atoms in the lattice. In the bee metals, interstitial impurities are usually present and might be expected to have various effects upon both flow behavior and recovery. For example, heterogeneous yielding might occur during prestraining. The diffusion of these interstitials can also relock dislocations during recovery so that a yield point might be obtained upon restraining (strain aging). Second, some of the bee metals (e.g., iron, molybdenum, and tungsten) undergo the familiar structure-sensitive ductility transition and exhibit brittle fracture at suitably low temperatures. It is of considerable interest to determine the effects of recovery on the transition temperature of such metals. The purpose of the present investigation was to extend our knowledge of flow-stress recovery to the bee metals and to study the effects of recovery on the ductile-brittle transition temperature. Unalloyed recrystallized are-cast molybdenum was chosen as a test material, since it exhibits a well-defined ductility transition near room temperature. As in the previous studies, the degree of recovery was measured in terms of the decrease of tensile flow stress. Prestraining and restraining were carried out at 150°C to avoid the possibility of brittle fracture. EXPERIMENTAL PROCEDURE The are-cast molybdenum sheet used in this investigation was obtained from the Climax Molybdenum Co. of Michigan. It was 0.060 in. thick by 10

Jan 1, 1964

The following is an extract of the Engineers' licensing law recently passed by the Colorado legislature; it went into force July 10. On the board of examiners are representatives of the four national societies. R. J. Grant, of Denver, represents the American Institute of Mining and Metallurgical Engineers; H. I. Reid, of Colorado Springs, the. American Society of Civil Engineers; H. S. Sands, of Denver, the American Institute of Electrical Engineers; and Frank E. Shepard, of Denver, the American Society of Mechanical Engineering. Within sixty clays after the taking effect of this act the Governor of the state shall appoint a State Board of Engineer Examiners, to be composed of five members, who shall be legal residents of the state of Colorado and who shall have been engaged in the practice of engineering for at least ten years. Upon the expiration of the term of any members other than the state engineer the governor shall appoint their successors for a term of four years, from a list of five nominees elected by the licensed engineers acting in a general assembly called together for this purpose by the president of the board. Such assembly shall be held in the month of January next preceding the expiration of the terms of any members. The Board of Examiners shall adopt all necessary rules, regulations and by-laws to govern its proceedings, not inconsistent with this act or the laws of the state or of the United States.

Jan 8, 1919

By U. Andres

U. Andres (The Technion, Haifa, Israel)-The authors are to be congratulated on their research, new and interesting, in a field which, however, the present writer and his assistants have been trying since 1962 to bring to the attention of the scientific and technical world, by means of publications covering several different aspects of this many-sided problem. We announced, in these publications, the results of magneto-hydrostatic (MHD) separation of magnetic and nonmagnetic minerals which we made in magnetic fluids (in paramagnetic solutions and suspensions of magnetic particles) which interact with permanent" and impermanent" inhomogeneous magnetic fields. There is no doubt that the authors have succeeded in creating ferrimagnetic colloids made by dispergation of 10-30 wt % of magnetite in kerosene in the presence of 7-10 vl % oleic acid. It may be judged by [Figs. 3 and 4] that the suspensions represent great stability systems and also "hysteresisless" fluids [(Fig. 5)] which bear witness to the existence of superparamagnetic suspensions. If the viscosity of these colloids is not so high, and the cost of preparing them can be covered, the fluids which have here been received can possibly be of interest to the technology of mineral separation. The potential possibility and technological perspective of similar media is demonstrated in our joint work with G. Bunin18 in 1965. The research carried out on the pushing out of cylinders and spheres from magnetic fluid is impressive; it would, however, have been interesting if the authors had compared their results with those on the pushing out of bodies from magnetic fluids adduced from our work." In my books" there happens to be described an experiment on the pushing out of a sphere in magnetic wedge field, in which the pushing out force of suspension with 5 vl % of magnetite reached 125 g per cc. This testifies to interesting possibilities of these media. Our works' shows also, on the basis of Laplace's equation the receiving of an interesting distribution of pushing out forces by selection of corresponding configurations of magnetic poles. Objection must be made to the authors' introduction of the term "antigravity force." The direction of this force does not depend on the direction of the gravity force and their opposition, i.e., antigravity is only one particular case. I am in full agreement with the authors' statement that magnetic pushing out forces "can be utilized to separate nonmagnetic objects according to variations in their densities." It is, however, necessary to make only one important addition, which can be found in our research on MHS at the Technion in Haifa, namely, that magnetic fluids in magnetic fields can be utilized in the separation of minerals according to variations in their magnetic susceptibility. The authors' conclusion is especially important considering the fact that in our publications" (including one in English") some designs of MHS separators and some technological results received on MHS-separators have already been described. S. E. Khalafalla and G. W. Reimers (Authors' Reply)We were aware (mostly through Chemical Abstracts of the American Chemical Society) of the use of solutions of paramagnetic salts such as manganous sulfate in agnetohydrodynamic separations by the Russian school headed by G. Bunin."n Professor Andres' contributions to this school are also evident in his application of the ponderomotive forces in an electrolyte placed in electric and magnetic cross-fields to separate coal and other useful minerals." It must be realized, however, that the foregoing research by Bunin et al." involved the use of magnetic fields and field gradients of very large magnitudes, i.e., such that H • grad H - 101 Oe2 per cm. The magnetization of paramagnetic salt solutions range from 0.1 to 0.5 gauss (at fields of a few thousand Oersteds) and never reach saturation. The magnetization of our superparamagnetic ferrofluids ranges from 100 to 500 gauss and reach saturation at fields of a few hundred Oersteds. Hence, to effect the same separation, the quantity "H

Jan 1, 1974

By C. Pin, J. Bruce Wagner

In order to demonstrate the role of defect chemistry in the solid state to a process-metallurgy reaction, laboratory experiments were carried aut to remove copper from liquid lead using lead sulfide which had been doped to provide definite concentrations of cation vacancies. The removal of copper decreases in the order: bismuth- or antimony-doped PbS, undoped PbS or tin-doped PbS, and silver-doped PbS. The data are explained using the simple mass -action law and in terms of the exceedingly rapid interstitial diffusion of coppw in PbS to vacant cation sites. Results are in agree-ment with thermodynamic predictions and certain industrial practices that copper may be removed from lead below the limit of its coexistence with pure Cu,S and pure PbS. The role of defects in solids has been exploited in semiconductors and many device applications, in explaining tarnish formation, dissolution rates, and mechanical properties. The application of these principles to many process-metallurgical problems has not received as much attention. It was the purpose of this study to illustrate the role of defect structures of solids in a process-metallurgical application. When lead is refined, the ore, galena (PbS), is reduced by a series of operations to liquid lead (lead bullion) containing impurities such as copper, bismuth, antimony, arsenic, and silver depending on the original composition, the fluxes added, and the particular type of operation, see Fig. 1. In order to produce a pure lead, a series of refining operations are carried out. A typical lead-bullion analysis before drossing is shown in Table I. Copper is removed first as its presence increases the zinc consumption during the desilverizing process. For preliminary copper removal the lead bullion is brought to a temperature of 440°C in a kettle of 60 metric tons capacity. Some tar (or sawdust or resins) is usually added and the kettle is cooled slowly to 400°C while the liquid is stirred. A solid phase, called a dross, floats on top of the liquid and the particles of the solid phase adhere to the tar. This "hot dross" is collected. It contains mostly lead and copper which are partly oxidized and/or sulfurized if the lead bullion contains some sulfur.*

Jan 1, 1963

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.' The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961

By W. C. Hagel

In 1952, Hauffe and pfeiffer1,2 reported that parabolic rates of nickel oxidation are decreased by factors of two and four at 1100° and 1000°C, respectively, when Li2O vapor is present. Hauffe 's3 explanation was that monovalent lithium enters the crystal lattice of p-type NiO to decrease cation-vacancy concentration and, hence, diffusion of Ni2+ ions across the growing oxide. After first succeeding in adding lithium directly to molten nickel, the purpose of this investigation was to determine whether alloyed lithium is a more effective oxidation inhibitor than the external vapor. Seven 650-g heats were prepared by melting carbonyl nickel inductively under 1 atm of argon. Various amounts of lithium were added by dropping small chunks into the melt. Only about 10-pct recovery was achieved with the remainder lost by spattering and volatilization. Nominal and actual

Jan 1, 1965

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By David White

IN these days, when detailed investigations of stratigraphy, structure, and sand conditions so frequently result in the discovery of new oil fields, and applause from oil companies and the public, geologists do well to walk humbly, and punctiliously to admit that the geologic principles controlling the distribution of oil and gas have as yet been discovered only in part, and that what remains yet to be learned is probably vastly more than what is already known. The few experiments already at-tempted have been fragmentary, and somewhat desultory, and however positive each of us may be with respect to certain theoretical conclusions, many of the fundamental questions as to the origin and mode of occurrence of petroleum are subject to radical disagreement. Of the chemical changes attending the generation of petroleum from organic matter, little is actually known. Most of the postulated formulas are liable to be misleading, through ignorance of essential factors. Open-mindedness is therefore a prime essential at the present stage of our science. Nevertheless, adopting the hypothesis that oil originates in some manner fundamentally connected with the organic theory, and in possible departure from such open-mindedness, the writer will pay no attention to the so-called inorganic theory, since every attempt to apply this theory to the study of old oil fields, or to the discovery of new ones, affords cumulative evidence of its inadequacy. In this paper, some of the factors affecting the occurrence of petroleum that the writer believes worthy of consideration by the prospector for oil in any new region will be discussed. Some of these, which are less generally understood, will be considered somewhat in detail. Other points, the significance of which cannot now be determined, require more field study, and for that reason are here brought to the attention of the field geologist. On the other hand, certain theoretical points which do not bear especially on the oil possibilities of a new region will be given little

Jan 2, 1920

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By A. M. Gaudin

A GREAT number of hypotheses has been advanced to explain the complex phenomena that are encountered in flotation. In the days of bulk-oil flotation, when a large quantity of oil was employed, it was observed that the oil-mineral aggregate floated above the ore-pulp because of its lesser density. With the advent of froth-flotation this phase of the theory had to be modified to take into account the presence of air bubbles. The reason why the mineral-bearing froth of today rises to the top of flotation cells is, of course, because the air-mineral aggregate, with whatever reagent may be associated with it, is lighter than the pulp. In an attempt to explain froth-flotation the fact has been emphasized that certain minerals are wetted and therefore remain in water; while others are not wetted and therefore become associated in preference with air. Such an "explanation" does not explain facts, it merely states them; for instance, it does not explain why minerals are wetted under some circumstances and not wetted under others. Going somewhat further, the wetting or nonwetting of minerals by water has been ascribed' to differences in the angles of contact between oil droplets and mineral surface at the surface of the minerals. This explanation, however, was abandoned when soluble flotation reagents came to replace the so-called "insoluble" reagents. Another theory, sponsored about 10 years ago by Ralston,2 involves the effects of electric charges at the surface of the minerals particles and air bubbles. This theory, unfortunately, was not developed as fully as it seems desirable.

Jan 1, 1927

By Robert T. MacMillan

Of all the mineral substances utilized by man, salt or sodium chloride has one of the longest and most varied histories. Because all animal life is descended from marine organisms, sodium and chlorine became necessary to life, and as sodium chloride meets requirements most readily, common salt has been essential to human and animal diets from earliest times. As civilization progressed, man learned to evaporate sea water and brines of saline lakes and springs to obtain salt, and gradually ceased to depend on the flesh of animals and the occasional salt outcrops or "salt licks" they frequented. He also learned that salt had a multitude of uses, particularly as a preservative of meat and other foods. The importance of salt in the minds of early men may be readily seen from many allusions in the Bible and other ancient writings. Expressions such as "not worth his salt," and "the salt of the earth" are deeply embedded in the English language. Salt has symbolized friendship, fidelity, purity, and hospitality. It has been used as currency; had religious significance; caused wars; and has been a favorite commodity for taxation. The English word "salary" stems from the Latin word for salt, in which Roman soldiers received part of their pay. Although salt today retains its dietary importance, it has thousands of other uses. Of each 100 pounds produced in the United States less than three pounds is for table use. The other 97 pounds goes for agricultural, industrial, and chemical uses. Fortunately, reserves of salt are enormous and reasonably well distributed on the face of the earth. The sea is an inexhaustible source of salt which may be had at prices which vary with climate and other factors. In addition, large underground salt deposits and many salt lakes, springs and playas are scattered throughout the world. Most countries have access to a salt supply, although some are more favored than others. Properties Crystallized sodium chloride or common salt is known as halite. Its molecular weight is 58.454 and it contains, by weight, 39.34 pct sodium and 60.66 pct chlorine. Alternate positions in the cubic lattice are occupied, respectively, by negative chloride and positive sodium ions; the crystal form is isometric. Crystallization from water produces concentric shells, and when broken, a crystal shows conchoidal fracture. Salt has a hardness of 2.5; its specific gravity ranges from 2.1 to 2.6 for rock salt and is 2.165 for the pure crystal. The refractive index is 1.554; it melts at 800.8 ± 0.5°C and boils at 1413°C. Its heat of fusion is 123.59 cal/ gram. Salt is transparent or translucent and highly diathermous. It is colorless when pure and has a vitreous luster. Salt containing traces of iron oxides has varying shades of yellow, orange, brown, pink, or red. The peculiar shade of red sometimes found in that produced by solar evaporation of sea water has been attributed to tiny organisms. Blue mottlings sometimes seen in halite crystals have been attributed to colloidal sodium. Salt is soluble in water to the extent of 35.7 parts per 100 parts of water at 0°C and 39.8 parts per 100 of water at 100°C. The small difference in solubility with increasing temperature is important in the economics of producing salt by evaporating brine. Salt has a negative heat of solution which is 1.281 kg-cal/ mole at 18°C in 200 moles of water.

Jan 1, 1960

By J. D. MacKenzie

THE world production of copper for the first eight months of 1927 shows an increase of 3 per cent over the same period in 1926. Since February of this year, however, production has been considerably curtailed. The United States reduction in the last four months has been offset by the increased South Ameri-can and Belgian Congo production. The United States is now producing 58 per cent of the world production, Chile and Peru 17.3 per cent, Belgian Congo 5 per cent. In 1926 the United States produced 54 per cent, Chile and Peru 16.3 per cent, Belgian Congo 6.3 per cent. Production, Tons 1917-largest war year 1,580,000 1925 1,581,000 1926-increase 3 per cent 1,628,000 1927-increase 3 per cent 1,670,000 Copper Producing Countries, 8 mo., 1927: Tons Per Cent United States 644,000 58.0 Chile and Peru 192,000 17.3 Europe 90,000 8.1 Belgian Congo 56,000 5.0 Japan 46,000 4.1 Mexico 30,000 2.7 Canada 23,000 2.1 Figures are not available for Spain and Portugal, which would probably precede Mexico.

Jan 12, 1927

By Philip Lindstrom

T he Radon mine is in the north end of the Big Indian mining district in San Juan County, Utah. Hecla Mining Co. operated the mine from early 1955 to early 1964 through an operating agreement with Federal Resources, Inc. Development consisted of a 3-compartment, 690-ft shaft, 4 main levels driven on the ore horizon and a haulage level below the ore. Evaluation of physical and economic factors showed that this flat-dipping ore occurrence could be mined by a low-cost coal mining method. The value of the deposit was high and unusual pre¬miums were possible by clean mining. Complete extraction without loss of ore pillars, minimum ore dilution and high production per man were obtained by longwall mining.

Jan 12, 1964

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.', ' Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds' of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies' of the slags, slag weights, the metal particle theory,' ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat' is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

Abbey, Robert Graham, District Mgr. The W W. Sly Mfg. Co,. 50 Church St, New York, N. Y. '21 Abbott, A. N., Mines Supt., Mazapil Copper Co., Ltd ..Concepcion del Oro, Zac., Mexico. '23 Abbott, Argyle Campbell, Dev. Dept, E I du Pont de Nemours & Co, Wilmington, Del. '29 Abbott, Clarence E., V.P, Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co, 1242 Brown-Marx Bldg, Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Elkhorn Div., Consolidation Coal Co, Jenkins, Ky. '15 Abeel, George H., Jr., Cons. Min. Engr Box 427, Santa Monica, Cal. '18 Abel, Albert E., Asst. to Pres, Valley Mould & Iron Corp Hubbard, Ohio. '19 Abel, Raymond L., Asst. Prof., Dept. of Pet Refin., Univ. of Pittsburgh Pittsburgh, Pa. '28 Abell, Leo M., Research Engr, Sullivan Concentrator Chapman Camp, B. C., Canada. '31 Abernathy, George Elmer, Prof. of Geol. & Min . Kansas State Teachers College, Pittsburg, Kans. '20 Aborn, Robert H., Research Lab, U. S. Steel Corp. Lincoln Highway, Kearny, N. J. '19 Abozeid, Mahmood, Dept. of Mines & Quarries Cairo, Egypt. '26 Abraham, Arthur W. Box 1466, Bakersfield, Cal. '20

Jan 1, 1923

By FRANK R. VAN

I. INTRODUCTION. IN the summer of 1908, R. B. Cochran, Superintendent of the Compania Metalurgica Mexicana at Sierra Mojada, Mexico, presented to the Department of Geology and Mineralogy at Case School of Applied Science an interesting series of silver-, copper-, and lead-ores from the Veta Rica mine. These ores contained several interesting minerals which were associated in a somewhat peculiar manner, so that I was impelled to make a closer study of their occurrence. The investigation has brought out several new facts concerning the geology of the district and the geological occurrence of the ores, and therefore has seemed worthy of record. Two papers have been published previously about the region, one by Chism1 in 1887, and the other by Malcolmson2 in 1902. These articles, however, treat of the district more from the stand-point of the metallurgist and mining engineer, and not much attention is devoted to its mineralogy and economic geology. II. GEOGRAPHICAL LOCATION OF THE DISTRICT. The Sierra Mojada is situated in the extreme western part of the State of Coahuila, near the Chihuahua boundary. It is reached best via the Mexican Central railroad from El Paso, Tex., to Escalon, Chihuahua, a distance of 494 miles. From this point, a branch line, the Mexican Northern railroad, runs 78 miles in a NE. direction to the mines, which are its northern terminus. The railroad was built about 1890, practically on account of the Sierra Mojada mining-district. 1 Sierra Mojada, Mexico, by Richard E. Chism, Trans., xv., 542 (1886-87). 2 The Sierra Mojada, Coahuila, Mexico, and Its Ore-Deposits, by James W. Malcomson, Tram., xxxii., 100 (1901).

Aug 1, 1912