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By W. M. Corse

AT THE TURN of the century the nonferrous alloy industry was awakening to the value of scientific metallurgy, and brass foundries and rolling mills began to establish their own research laboratories for scientific research and control. As the industry grew and its scope broadened it became apparent that an organization was needed that would stand in the same relation to the nonferrous industry as the American Foundrymen's Association did to the iron foundry business. The brass founders' group of the foundrymen's association discussed the matter and it was finally decided to appoint a com- mittee to draw up a constitution for a new organization to be known as the American Brass Founders' Association. Charles J. Caley was chairman and Dr. Richard Moldenke secretary of this committee. The object of the organization as defined by the constitution was the study of the technological development of alloying and founding non- ferrous metals, and furthering the advance of nonferrous metallurgy and the standardization of materials and operations in cooperation with the Bureau of Standards and engineering societies.

Jan 1, 1932

Andy H. Vassiliou – Introduction Ladies and gentlemen,.good evening and welcome to the Paul F. Kerr Memorial Symposium dinner. I believe we are all here to honor the memory of a great teacher and advisor, and a true friend -- Professor Kerr, or Dr. Kerr, or to most of us who were his students, "Pappy" Kerr. Most of us who attended the Paul F. Kerr Memorial Symposium earlier today at the New York Hilton had the opportunity to read, or listen to, or discuss scientific papers presented in honor of Dr. Kerr. In addition, all of the speakers had the opportunity to reminisce about their association with Dr. Kerr, who was credited as having contributed substantially to their graduate education and the development of their careers. Dr. Kerr's two daughters -- Ruth and Nancy -- who attended the Symposium at the Hilton are also here with us tonight. I think we should keep tonight's festivities on an informal basis since we are all old friends or former students of Dr. Kerr. Some of us may want to say a few words about our experiences at the time we were students at Columbia, and hopefully include some anecdotes relating to Professor Kerr. I would like to invite everyone to do so, but first we have arranged for two of us to be the lead speakers, whom I will introduce in a few moments.

Jan 1, 1985

Upon the recommendation of its Technical Committee, The Com-pressed Air Society has adopted the following definitions of, certain terms. Displacement.-The displacement of an air compressor is the volume displaced by the net area of the compressor piston. Capacity.-The capacity should be expressed in cubic feet per minute, and is the actual amount of air compressed and delivered, expressed in terms of free air at intake temperature and at the pressure of dry air at the suction. Volumetric Efficiency.-Volumetric efficiency is the ratio of the capacity to the displacement of the compressor, all as defined above. Compression Efficiency.-Compression efficiency is the ratio of the work required to compress isothermally all the air delivered by an air compressor to the work actually clone within the compressor cylinder, as shown by indicator cards, and may he expressed is the product of the volumetric efficiency (the intake pressure and the hyperbolic logarithm of the ratio of compression), all divided by the indicated mean effective pressure within the air cylinder or cylinders.

Jan 8, 1918

By Robert Glass Cleland

WALTER DOUGLAS succeeded his father, Dr. James Douglas, as president of Phelps Dodge in 1916. Before assuming office, the new president had been assayer at Bisbee, superintendent of the Copper Queen, general manager of all the Phelps Dodge mining interests, and altogether had spent a full quarter of a century in various phases of the company's business. Energetic and imaginative, experienced and courageous, he had need of all these qualities before he surrendered the direction of affairs into younger hands, fourteen years later. For the period of his administration was one of sudden ebb apd flow, flush production, drastic curtailment, quick recovery, and near-disaster. In 1917, soon after Walter Douglas became president, Phelps, Dodge & Co., Inc., which had been formed in 1908 as a holding company, went through an internal reorganization for the purpose of simplifying the structure and changing it from a holding company to an operating company. The Copper Queen Consolidated Mining Company, which had the necessary charter power and authority to carry on the business of any and all the subsidiary com-

Jan 1, 1952

By Paul Billingsley

IN THEIR course across Ecuador, the Andes fail to show the mineral wealth with which they abound in Peru, Bolivia, and Chile. This may well be due merely to the concealment of recent volcanic ash and dense tropical jungle, but at any rate Ecuador has lacked the stimulation to development and progress afforded to the southern countries by the mines of Cerro de Pasco, Potosi, etc. 1 There is, however; in Ecuador, near its southern border, one mining district that, in recent years under North American management, has become a steady producer of mineral. wealth and. a community in which the sanitary and mechanical elements of modern life are displayed, for ;the first time, to the Ecuadorians of the lowland forests. The mining district of Zaruma is .situated in the province of El Oro, near the southwestern corner of Ecuador, about 50 km. (31 mi.) from the coast. Pizarro's first landing on the mainland was at Tumbez, at the mouth of the river that drains the Zaruma area; and the gold so abundantly found in this Indian town was soon traced to its source. In 1549, Mercadillo, one of the original (band, reached Zaruma, having worked his way up-stream through canyons that .are now regarded as impassable. The Spaniards proved themselves efficient prospectors, finding practically every orebody in the district as yet discovered; and, working

Jan 10, 1925

By Henry J. Miller, Marcella Linderman

During some experiments made by Henry J. Miller, partly in Germany and partly in the United States, in which it was found necessary to melt metals in quantities up to 60 kg. in a vacuum or under low pressures of hydrogen, molybdenum was tried as the resistor in the electric melting furnaces. Molybdenum ribbons 16 by 0.55 mm. and 18 by 0.45 mm. were used as resistors. The furnaces were of the type shown in Fig. 1. About the heating tube, Y, are wound parallel resistors of molybdenum ribbon from the water-cooled electrodes, El, Ez. The whole is within a copper container having outlets for the removal or introduction of gases and a window, W, for observation, the space about the heating tube and electrodes being filled with insulating material. The life of the molybdenum used as the resistor was found to depend very much on the manner of using it, its failure being due in some cases to thinning by evaporation or chemical reaction and in others to hardening, which prevented it from following the expansions and shrinking of the heating tubing without cracking. As such failures are often rather expensive in commercial work, it was thought worth while to determine the causes. The factors influencing the behavior of molybdenum resistors used in this manner may be briefly stated as follows:

By R. W. Jigins

OPERATIONS of the Braden Copper Co. are in the Chilean Andes, southeast of Santiago. Most remote of the company communities is Sewell, a town of 12,000 people, 7000 ft above sea level at the junction of the Coya and Teniente rivers. Four miles down the Coya River is the smelter town of Caletones, elevation 4500 ft, with a population of about 3000. At the junction of the Coya and Cachapoal rivers 24 miles below Sewell is Coya, eleva- tion 2500 ft, location of the company's two hydro- electric plants. The principal accounting offices; steel, iron, and brass foundries; railroad shops; and major mechanical repair and fabricating shops are at Rancagua in the central Chilean valley, 44 miles from Sewell. The company owned narrow-gage railroad connects with the Chilean national railroad at Rancagua and above Coya is the only modern means of travel. El Teniente mine at Sewell is the largest under- ground copper mine in the world. The mill, at the portal of the main tunnel, has a capacity of 34,000 tons of crude ore daily, although production is lower during the winter beacause of electric power restrictions. When operating at capacity the mill produces 2000 tpd of copper concentrates and 32,000 tpd of tailings. Tonnage of tailings is equivalent to about 100,000 tons of pulp at normal water to solid ratio.

Jan 10, 1957

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K&apos; = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys&apos;10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By J. D. Verhoeven

In the past 15 years a considerable amount of experimental and theoretical work has been done concerning the onset of convection in liquids as a result of interm1 density gradients. This work, which has been doue in many different fields, is reviewed here and extended slightly to give a rrlore quantitative understanding to the probletrz of conzection in liquid metal dlffusion experinletzts. In liquid metal systems the capillary reservoir technique is currently used, almost exclusively, to measure diffusion coefficients. In this technique it is necessary that the liquid be stagnant in order to avoid mixing by means of convection currents. Convective mixing may result from: 1) convection produced as a result of the initial immersion of the capillary; 2) convection produced in the region of the capillary mouth as the result of the stirring frequency used to avoid solute buildup in the reservoir near the capillary mouth; 3) convection produced during solidification as a result of the volume change; and 4) convection produced as a result of local density differences within the liquid in the capillary. The first three types of convection have been discussed elsewhere1-a and are only mentioned for completeness here. This work is concerned only with the fourth type of convection. Local density differences will arise within the liquid as a result of either a temperature gradient or a concentration gradient. It is usually, but not always, recognized by those employing the capillary reservoir technique that the top of the capillary should be kept slightly hotter than the bottom and that the light element should be made to migrate downward in order to avoid convection. In the past 15 years a considerable amount of work, both theoretical and experimental, has been done in a number of different fields which bear on this problem. This work is reviewed here and extended slightly in an effort to give a more quantitative understanding of the convective motion produced in vertical capillaries by local density differences. The Stokes-Navier equations for an incompressible fluid of constant viscosity in a gravitational field may be written as: %L + (v?)v = - ?£ + Wv - g£ [1] where F is the velocity, t the time, P the pressure, p the density, v the kinematic viscosity, g the gravitational acceleration, and k a unit vector in the vertical direction. A successful diffusion experiment requires the liquid to be motionless, and under this condition Eq. [I] becomes: where a is the thermal expansion coefficient [a =-(l/po)(dp/d)], a&apos; is a solute expansion coefficient [a&apos; = -(l/po)(dp/d)], and the solute is taken as that component which makes a&apos; a positive number. Combining with Eq. [3] the following restriction is obtained: Since there is no fixed relation between VT and VC in a binary diffusion experiment, Eq. [5] shows that the condition of fluid motionlessness requires both the temperature gradient and the concentration gradient to be vertically directed. Given this condition of a density gradient in the vertical direction only, it is obvious that, as this vertical density gradient increases from negative to positive values, the motionless liquid will eventually become unstable and convective movement will begin. The classical treatment of this type of instability problem was given by aleih&apos; in 1916 for the case of a thin fluid film of infinite horizontal extent; and a very comprehensive text has recently been written on the subject by handrasekhar.&apos; It is found that convective motion does not begin until a dimensionless number involving the density gradient exceeds a certain critical value. This dimensionless number is generally referred to as the Rayleigh number, R, and it is equal to the product of the Prandtl and Grashof numbers. For the sake of clarity a distinction will be made between two types of free convection produced by internal density gradients. In the first case a density gradient is present in the vertical direction only, and, since the convection begins only after a critical gradient is attained, this case will be called threshold convection. In the second case a horizontal density gradient is present and in this case a finite convection velocity is produced by a finite density gradient so that it will be termed thresholdless convection. Some experimentalists have performed diffusion experiments using capillaries which were placed in a horizontal or inclined position in order to avoid convection. These positions do put the small capillary dimension in the vertical direction and, consequently, they would be less prone to threshold convection than the vertical position. However, if the diffusion process produced a density variation, as it usually does, it would not be theoretically possible to avoid thresh-

Jan 1, 1969

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.&apos; Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"&apos; are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".&apos;" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.&apos;" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

W. G. MATTESON, Houston, Tex.-I think that Mr. Powers has given us some very valuable information on the Healdton field, which is of material interest in view of the fact that the Healdton field has passed Cushing in the point of production, and if not leading, stands second only to the new El Dorado field in the point of production of the oil-in this country. Mr. Powers says that the deepest producing sand at Healdton is 1860 ft. Within the last 3 or. 4 months they have drilled to 2700 ft. there and found a sand which is producing very high-grade oil, if I remember correctly, about 42 gravity. Another very important point brought out by Mr. Powers is the fact that the Pennsylvanian beds and the Permian beds are conformable according to his interpretation. He seems to have based his interpretation upon the gathering of a number of well logs and a very careful study of them, but it seems to me the information furnished by the, well logs is really insufficient to justify such an important conclusion. In the first place, the difficulty of interpreting the line of demarcation between the Permian "Red Beds" of Oklahoma and the top of the Pennsylvanian is apparent, for the reason that sometimes the uppermost Pennsylvanian formation has a reddish phase and the line of demarcation is not very sharp.

Jan 4, 1918

By Arthur B. Foote

Ore production from the property of the Miami Copper Co. began early in 1911. Until 1925 this ore came from the so-called high-grade orebodies, which contained a little over 2 per cent. copper. This ore was mined by the following methods: 1. Top slicing after mining the peaks by square setting, which produced 4,524,347 tons, including ore from square setting. 2. Shrinkage stoping with sublevel caving of the pillars, which produced 2,230,577 tons. 3. Undercut caving with hand tramming, which produced 15,427,672 tons. Estimating December tonnage, the total ore mined to the end of 1929 will amount to slightly more than 43,000,000 tons. The first method was described by E. G. Deane&apos; and the second by D. B. Scott,&apos; and the third, together with a general description of the mine, by J. H. Hensley, Jr.&apos; The geology of the district has been worked out by Dr. F. L. Ransome.2 The author acknowledges also the assistance of R. W. Hughes, assistant mine superintendent, E. V. Graybeal, chief mine engineer, A. J. McDermid and S. R. Burdick, engineers of Miami Copper Co., Miami, Arizona. Factors Influencing Selection of Mining Methods The mining method described herein was selected primarily with a low mining cost in view and was developed to avoid as far as possible dilution of the already very low-grade ore. In 1924, with the exhaustion of the high-grade orebodies in sight, it was decided to develop the low-grade orebody, which at that time contained 36,000,000 tons of ore assaying 1.06 per cent. copper, and had an area of 50 acres with an average thickness of 206 ft. overlain by an average thickness of 320 ft. of barren capping.

Jan 1, 1930

By Zay Jeffries

It has been known for centuries that iron and steel could be hardened by cold hammering and that the metal could be restored to the normal condition by heating to a red heat arid cooling, either rapidly or slowly with nearly pure iron, but slowly with steels containing considerable carbon. The art of tempering steels is also very old. When a medium- or high-carbon steel is quenched from a cherry-red heat, the hardness is increased; this hardness can be reduced by heating to various temperatures below the lower thermal critical point,, which is near 700" C. The present paper will not consider these old and well known changes in iron and steel below the thermal critical range but will confine itself to the more unusual changes, some of which have been studied recently. Stromeyer,1 for example, In 1886, reports that both working steel and heat treatment of steel in the blue-heat range arc highly injurious. Recently, however, some metallurgists believe that the straiglltening of warped steel forgings at a blue heat produces a beneficial effect on the metal2 The Engineering Division of the National Research Council has constituted a committee on Physical Changes in Iron and Steel below the Thermal Critical Range, which has the following personnel: K. R. -Abbott, H. C. Boynton, William Campbell, J. V. Emmons, F. B. Foley, H. J. French, H. M. Howe, Zay Jeffries (chairman), F. C. Langenberg, J. A. Mathews, P. D. Merica, A. H. Miller, J. H. Nelson, G. A. Reinhardt, W. E. Ruder, H. F. Wood. This committee is studying several aspects of the physical changes in iron and steel. The results, reported in the literature and obtained by recent experimentation, will be given; this will be followed by a general theoretical discussion of the more important

Jan 1, 1922

By Zay Jeffries

It has been known for centuries that iron and steel could be hardened by cold hammering and that the metal could be restored to the normal condition by heating to a red heat arid cooling, either rapidly or slowly with nearly pure iron, but slowly with steels containing considerable carbon. The art of tempering steels is also very old. When a medium- or high-carbon steel is quenched from a cherry-red heat, the hardness is increased; this hardness can be reduced by heating to various temperatures below the lower thermal critical point,, which is near 700" C. The present paper will not consider these old and well known changes in iron and steel below the thermal critical range but will confine itself to the more unusual changes, some of which have been studied recently. Stromeyer,1 for example, In 1886, reports that both working steel and heat treatment of steel in the blue-heat range arc highly injurious. Recently, however, some metallurgists believe that the straiglltening of warped steel forgings at a blue heat produces a beneficial effect on the metal2 The Engineering Division of the National Research Council has constituted a committee on Physical Changes in Iron and Steel below the Thermal Critical Range, which has the following personnel: K. R. -Abbott, H. C. Boynton, William Campbell, J. V. Emmons, F. B. Foley, H. J. French, H. M. Howe, Zay Jeffries (chairman), F. C. Langenberg, J. A. Mathews, P. D. Merica, A. H. Miller, J. H. Nelson, G. A. Reinhardt, W. E. Ruder, H. F. Wood. This committee is studying several aspects of the physical changes in iron and steel. The results, reported in the literature and obtained by recent experimentation, will be given; this will be followed by a general theoretical discussion of the more important

Jan 1, 1922

By W. G. Matteson

I. Introduction...................................................... 436 (a) Extent of the Gulf Coastal Plain. (b) History of Important Gulf Coast Oil Pools. 1. Corsicans, Tex. 2. Spindletop, Tex. 3. Sour Lake, Tex. 4. Jennings, La. 5. Saratoga, Tex. 6. Batson, Tex. 7. Humble, Tex. 8. Caddo, La. 9. Vinton, La. 10. Naborton, La. 11. Red River, La. 12. Edgerly, La. 13. Goose Creek, Tex. 14. Damon Mound, Tex. 15. New Iberia, La. (c) Favorable Features of the Gulf Coast Pools. 11. General Topography and Physiography of the Gulf Coastal Plain.....440 111. General Stratigraphy of the Gulf Coastal Plain West of the 90th Meridian......................................................441 IV. Structural Types and their Characteristics.........................446 (a) hnticlinal Structure. (b) Structure of Salt Domes. 1. Domes of the Coast Prairie. 2. Domes of the Wold Region. 3. Recapitulation of Dome Structural Characteristics. V. Methods of Surveying and Prospecting............................. 454 VI. The Development of Salt Domes................- .................458 VII. Origin of Salt Domes...............4.............................461 (a) The Volcanic-plug Theory of Hager. (b) The Contemporaneous Sedimentation Theory of Norton. (c) The Theory of Upward Pressure Exerted by the Force of Growing Crystals, as Developed by Harris. VIII. Source of the Oil in the Gulf Coastal Pools.........................465 IX. Petrolific Value of the Salt Domes of the Wold Region..............467 X. Future Outlook.................................................. 467

Jan 1, 1918

By Hugh Neill, O&apos

In previous papers,&apos; the author has reported the results of experiments on the straining in tension of a single-crystal test piece, about 0.6 in. long, of vacuum-melted electrolytic iron containing 1.8 per cent. of silicon. The crystal was originally in the "as cast" condition, and was stressed slowly along a tetragonal axis so that slipping along conjugate gliding planes finally transformed the original cylindrical portion into a pair of fracture wedges. One of these fracture wedges was sectioned along the stress axis in a plane at right angles to the edge of the wedge. A metallographic study of this plane of section led to the conclusion that slip had taken place in the (111) direction along (112) planes making a V shape with the stress axis. The present paper describes the results of scratch-hardness tests conducted on the same section, in order to determine the distribution of strain hardness therein, followed by annealing, and considers the resulting variations in hardness. These observations supplement those made by Krivobok2 on similar material reduced 25 per cent. by hammering (i. e., by impact) in the cold. In order to investigate ageing effects, two small crystals of the same alloy were also tested. The Specimens Employed The principal specimen, A, was prepared for the metallographic examination leading to the determination of the slip planes of the crystal. Therefore the work described in this paper was conducted on metal which had been repeatedly etched and had been allowed to rest for about 30 months after straining. It consisted of a section of the fracture wedge and contiguous unstrained head of the test piece taken along a tetragonal axis parallel to the direction of stressing, the plane of section originally being not far removed from the (011). Several subsequent grindings