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By Dwight C. Roberts, Stender Sweeney

The spacing of wells in Long Beach oil field has caused much discussion from the earliest days of its development, on account of the closely drilled town-lot areas which have been as intensively developed as any productive areas in the world. The purpose of this paper is to present the results obtained from this type of development in comparison with the more widely spaced development in this field, now that a sufficient length of productive life has elapsed. The intensity of development in Long Beach is indicated by the fact that up to Sept. 1, 1929, there were 1736 wells either drilled or drilling. Of these 165 failed to get production and 121 were drilling. Thus 1450 wells have produced oil from an area of 1350 acres. Up to July 1, 1929, these wells produced a total of 35.5,047,913 barrels. Method Pursued Four groups of offset areas were chosen, in each group the wells in one area are widely spaced and in the other, closely spaced. The areas in each group are contiguous and the groups are spread over the field from the southeast end to the northwest, so that representative data are assured. The comparison has also been extended to shallow and deep zones, like zones in their respective areas being compared. Even though these productive zones are very thick, a fair picture of results is obtained, because the drilling of the wells in the two types of areas was concurrent in the different groups and, as a rule, the thickness of sand opened up at any one time was about the same. As deeper sands were found, wells in offset areas were deepened or new ones were drilled in both types of areas. The division of zones was made in the same manner in contiguous areas. The total cumulative production up to July 1, 1929, of the wells in their respective zones in each area was obtained. From these figures were computed the recovery per well, recovery per acre, acreage per well, and the ratios of these factors. Thus July 1, 1929, is the end of the period considered in all areas.

Jan 1, 1930

By C. E. Reistle, G. L. Nye

The East Texas field is in Smith, Rusk, Gregg, Upshur and Cherokee counties, Texas. The discovery well was completed Sept. 8, 1930, near the eastern limit of the field. Within less than one year the new field became the dominant factor in the world production of crude oil. On Aug. 16, 1931, eleven months after completion of the discovery well, there were 1644 wells in the field, and the average daily production was 584,475 bbl. Since that time the number of wells has increased to 8195 on Oct. 1, 1933, and the field has produced 385,979,691 bbl. of oil. The geology of the East Texas field has been discussed by Lahee,1 Levorsen,2 Minor and Hanna3 and others, and it will not be discussed in detail here. The field is a structure of the monocline type on the westward dipping homocline between the Sabine uplift and the East Texas geosyncline. Production is obtained from the Woodbine group, which has been truncated and then sealed by the Austin chalk, which rests unconformably upon it. The oil-saturated part of the sand lies bettween a sub-sea depth of 3050 ft. on the east side of the field, where the Woodbine sand stops and the Austin chalk rests directly upon older formations, and a sub-sea depth of 3320 ft., which was the average depth of the water table in the sand at the time the field was discovered. The field is about 40 miles long and has an average width of approximately 4 1/2 miles. The area within the proven limits of the field is close to 116,580 acres and the normal Woodbine water underlies nearly 62,000 acres on the western side of the field at the present time. The field is unusual in several respects: (1) the tremendous size of the reservoir system and the quantity of oil in place; (2) the large area of the oil and water contact, which makes water movement possible into the oil-bearing part of the structure; (3) the absence of free gas within the main producing sand of the field. Changes in the reservoir pressure during the production history of the field have been greatly affected by

Jan 1, 1934

By J. H. Wiggins

Granting that about 600,000,000 bbl. of light oil will be produced in the United States this year and taking the Bureau of Mines' statement that 71/2 per cent. of the total crude production will be lost before the finished gasoline is shipped from the refinery, the volumetric evaporation will be 45,000,000 bbl. of the cream of the gasoline. This is a ConseNative figure and is equivalent to 1,890,000,000 gal. The real value of this liquid is at least 150 per cent. of the value of an equal volume of motor fuel. At only 10 c. per gal., the value lost is $189,000,000; at 15 e. per gal. the loss is $283,000,000. If 750,000,000 bbl. of light and heavy oil are produced here this year and the average price per barrel is $1.333, the gross return to producers will be $1,000,000,000 and the net returns about $200,000,000, if the cost of production is only $1 per barrel. Thus, the evaporation bill is about 20 per cent. of the gross income and is equal to the net income of the crude-oil producers. Two other comparisons with popular phases of the petroleum industry will help give an adequate conception of the evaporation problem. These are: cost of preventing evaporation compared to cost of cracked gasoline and volume of gasoline evaporated compared to volume of gasoline manufactured from natural gas. When gasoline is manufactured from heavy oils by the cracking process, there are two important divisions of the total cost of the product: the manufacturing cost, such as plant cost, operation, maintenance, etc., and the cost of the barrel of heavy oil, from which the cracked gasoline is made. In preventing evaporation loss the cost first mentioned enters into the total cost, but the second cost is eliminated; that is, no charge is necessary for stock from which to manufacture the saving. A detailed analysis of these two costs on a large scale shows that the net income from a dollar spent in preventing evaporation loss from the lease through the refinery is twice the net income from a dollar spent in cracking. Of

Jan 1, 1924

By C. W. Mason

TIN has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphur. The notorious "tin disease," which Cohen1 has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white 0 tin to cubic gray a tin, has apparently encouraged the expectation that one or more addi-tional polymorphic modifications might exist. The search for confirma-tion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but for previous assumptions. The ball apparently was started rolling in 1880 by Trechmann,' who reported a new modification of tin (y tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be y tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller.3 Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,6 by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) and stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencer3 in 1921 examined the above evidence critically; he found similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on a second lot of crystals, not described crystallographically.)

Jan 1, 1939

By L. P. Teas

The main facts brought out by the study of the blende-bearing ores examined are as follows: 1. Chalcopyrite as minute triangular or rectangular dots, or as

Jan 1, 1918

By C. E. Ells, A. Sawatzky

The effect of neutron irradiation on tensile properties of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy has been evaluated for integrated neutron fluxes up to 3 x 1020 n per sq cm (E > 1 Mev). Specimen temperature during irradiation was normally 300°C. The material was studied both in annealed and in quenched and aged conditions. When the alloy (fab-ricatedfrom sponge zirconium) is quenched from a temperature =40°C below the a + ß/ß transformation and aged 6 hr at 535oC, neutron irradiation up to the maximum studied has little effect 071 reduction in area, although there is a drop in uniform elongation and the yield strength is increased by = 25 pct. Conversely, irradiation of the alloy in an annealed condition can result in much greater changes in properties, with yield-strength increases of up to 200 pet. The dose dependence of irradiation hardening obeys the saturation equntion proposed by Makin and Minter to explain hardening in copper and nickel: Act = C[1 - exp(-Døt)/1/2 A rnodel is proposed to explain the effect of niobium content and metallurgical condition on irradiatiotz behavior. THE Zr-Nb alloys form a class of material susceptible to marked strengthening by quench and age heat treatment. With niobium concentrations as low as 2.5 wt pet, strengths can be developed which are double those of annealed zircaloy-2.1 Since the neutron-capture cross section of the Zr-2.5 wt pet Nb alloy is nearly identical to that of Zircaloy-2, significant gains in power-reactor neutron economy could be obtained by replacing stressed in-reactor components of Zircaloy-2 with the heat-treated Zr-Nb alloy. When the solution heat-treatment temperature is in the high (a + ß) phase, then the tensile properties of the quenched (and aged at 500°C) material have been shown to be relatively insensitive to neutron irradiation.1-3 Addition of small quantities of copper to the binary Zr-2.5 wt pet Nb alloy gives a useful reduction to the corrosion rate in air and carbon di- oxide,&apos; and a ternary alloy of composition Zr-2.5 wt pet Nb-0.5 wt pet Cu was chosen for one component in the Douglas Point Reactor. This application utilizes both the corrosion resistance to a moist air-carbon dioxide environment and the strength developed by a quench and age heat treatment. By suitable choice of solution heat treatment and aging temperatures, tensile properties of the ternary alloy can be made nearly identical to those considered as optimum for the binary alloy. One effect of the copper addition, however, is to give marked changes in the aging kinetics of the alloy.&apos; For this reason, it appeared that neutron irradiation might promote overaging in the ternary alloy, particularly at the elevated service temperature (=300°C). This paper describes the effect of neutron irradiation on the tensile behavior of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy in several metallurgical conditions pertinent to its use as a reactor material. The metallurgical conditions included those for which aging occurs in the unirradiated material, and fully annealed conditions for which a higher degree of thermal stability could be expected. 1) EXPERIMENTAL Two batches of alloy were used, both made from sponge zirconium. The fabricator&apos;s analysis of principle constituents showed no significant difference between the two batches, Table I. The rod material was rolled to 1.5 in. diam, and then swaged to final sizes of 0.5 to 0.375 in. diam at nominal temperatures of 785" and 625°C for the AM and AS batches, respectively. Subsequent hydrogen analyses at CRNL confirmed that the hydrogen concentration of the as-received rod was indeed <20 ppm. However, it was found that the (a + ß)/ß transus for the AM material was approximately 25°C lower than that of the AS material, indicating rather more difference in oxygen concentration than given in Table I. Except for a small difference in yield-point behavior, the tensile prop-

Jan 1, 1965

By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10&apos; C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm &apos;C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.&apos; in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;&apos;-&apos; and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By John E. Hockett

The need for basic information about the relationship between resistance to dejormatim (flow stress), temperature, strain, and strain rate, for the solution of metal-fovming problems, is pointed out. Some early attempts to satisfy the need are mentioned. A brief description of a machine called a Cam Plastome-ter is given, including the processing of results of testing in the machine. Next, a program of testing aluminum in compression over a wide range of constant true-strain rates (0.1 to > 200 sec-1) and a modevately broad range of temperatures (223° to 673°K) is described. The results of this program are presented in the form of true-stress us true-strain cuvves. The data in these curves are presented in the form of relationships between true stress and true-strain rate in sermilogarithmic and log-log form, as functions of temperatures—for several true strains. Finally, true stress, for a given true strain, is displayed as a function of log true-strain rate and absolute temperature, i.e., a surface. SINCE the publication of Hill&apos;s book1 on plasticity theory, increasingly rapid advances have been made in analytical solutions to forming problems. Methods in common use are the slab method, the uniform deformation energy method, the limit analysis method, the slipline field method, and the semiexperimental method called "visioplasticity". These approaches, and examples of their use, are covered in detail by Johnson and Melloor2 and by Thornsen, Yang, and Kobayashi.3 unfortunately, practically all of the above work has had to rely upon a number of basic assumptions, e.g., homogeneous deformation and Coulomb (sliding) friction; and virtually no dependence of the mechanical behavior of the deforming metal, upon temperature, strain, and strain rate, has been included. It is with this dependency that this paper is concerned. Loizou and sims4 looked at the above relationship for lead using both a constant compression-speed Cam Plastometer and a constant true-strain-rate Cam Plastometer designed by Orowan.5 Alder and Phillips8 investigated the relationships for aluminum, copper, and steel in the same constant true-strain-rate Plastometer. cook7 tested twelve steels at temperatures ranging from 1170° to 1473°K in the same Plastometer over a range of true-strain rates of 1.5 to 100 sec-&apos;. The writer tested commercially pure aluminum at room temperature and depleted uranium at temperatures from 573" to 873°K at strain rates from 10-3 to 1.0 sec-1 in a Cam Plastometer designed and built at Los Alamos Scientific Laboratory.8 During the past few years the Cam Plastometer at Los Alamos has been used for a number of relatively minor experiments on brass, mild steel, duralumin, Armco iron, and depleted uranium. In this time the machine has been continually modified and improved. It was decided to utilize fully the wide range of strain rates now available with the machine by testing a material about which some information was already in the literature. Prior work on commercially pure aluminum6 appeared to deserve confirmation and expansion. So it was decided to explore the resistance to compression of this material over the currently available range of constant true-strain rates and a convenient range of temperatures. This paper is a report of that exploration. I) EQUIPMENT AND PROCEDURE The principal item of equipment is, of course, the Cam Plastometer, the working part of which is shown in Fig. 1. In this figure, an aluminum specimen may be seen between two tungsten carbide platens, in position for a room-temperature test. Above the upper carbide platen is a load cell. Output from the load cell is amplified and applied to a galvanometer in a recording oscillograph. Auxiliary equipment includes the oscillograph, the control console, a counter, and a time-mark generator. The counter is first used in adjusting the time base. Then it registers the count, of sixty pips per revolution generated by the rotating cam, in each second. These pips and the time base are also applied to galvanometers in the oscillograph. Thus, load, time, and cam position are recorded simultaneously. Heating of a specimen prior to compression is done

Jan 1, 1968

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By G. T. Hahn, C. N. Reid, A. Gilbert

An evaluation is made of the possible cautsal relationship between twinning and fracture in molybdenum. For both single and poly crystalline material no instance of twin-induced fracture was observed. Instead brittle fracture was found to be slip-induced at heterogeneities. For single-crystal material, the yield stvess in compression and the fracture stvess in tensiow obey a similar angular- relationship which follows approximately a 1/cos2 ? law. where 0 is the angle between the specimen axis and the nearest (100) plane. This sittlilarity between yield and fracture behavior casts doubt on the interpretations made previoltsly that a 1/cos2? relationship supports a critical normal fracture stress criterion. SINCE fracture in brittle materials takes place at stresses an order of magnitude lower than the theoretical strength of the lattice, it must be postulated that some stress-concentrating effect is operative during the fracture-initiation process. Several mechanisms have been proposed whereby the necessary stress concentrations could be produced. The well-known Cottrell mechanism1 describes a dislocation interaction which can lead to the formation of an incipient cleavage crack on a cleavage plane, and both zener2 and stroh3 have discussed models which predict the stress concentration at the intersection of a slip band with a grain boundary. When twinning occurs twin/twin intersections and twin/grain boundary intersections represent another possible means of fracture initiation. Although still controversial, the concept of twin-induced fracture is supported by a weighty mass of evidence, which has been reviewed in a recent paper.4 This investigation was conducted in order to assess the extent to which the brittleness of molybdenum can be ascribed to this cause. Emphasis was placed on seeking direct metallographic evidence for twin-induced fracture such as arrangements of twins located at the fracture origin. EXPERIMENTAL PROGRAM Materials. The experimental materials are described inTable I. From the chemical analyses and estimates of the amounts of interstitials likely to be retained in solution,5 it is concluded that all were mul-tiphased systems. X-ray diffraction experiments6 showed no evidence of preferred orientation in the polycrystalline materials. Single crystals were grown from Molybdenum X and Y using the floating-zone technique,&apos; in a vacuum of better than 3 x 10-5 Torr. However difficulties were experienced with Molybdenum X due to violent gas evolution from the molten zone, and additional crystals (Crystals 3 to 6) were produced by annealing for 5 1/2 hr at 2300°C under a vacuum of 10-4 Torr. Techniques. A series of tension, compression, and bend tests was conducted. Tension tests were used to demonstrate brittle behavior, to measure brittle-fracture stresses, and to provide fractured specimens for metallographic inspection. Compression tests were employed in order to obtain some ductility and a measure of the yield stress. Furthermore, it was considered that compression loading would permit the study of crack nucleation in the absence of propagation. The bend tests were conducted to facilitate identification of the fracture origin, which would be expected to be at, or near, the tensile surface of the sample. Tests were carried out at temperatures between 78" and 298°K attained by means of a liquid-nitrogen evaporator of modified Wessel design.&apos; Specimens were fashioned by mechanical grinding, and, prior to heat treatment, were electropolished at 10 v in a 3:l mixture of ethyl alcohol and sulfuric acid, using a stainless-steel cathode. Except where noted, a strain rate of 4 pct per min was used. All specimens had a gage section 0.75 in. long; diameters of 0.10 and 0.20 in. were adopted for the tension and compression specimens, respectively, the former of single shoulder design, the ends being gripped in split collets with a conical bearing surface. In the bend test, electropolished specimens measuring 0.080 by 0.25 by 1.25 in. were deformed at 78°K by four-point loading. The bending device had spans of 1 in. between the outer and 4 in between the inner fulcra; it was stressed between the compression anvils of the Instron machine at a constant deflection rate. EXPERIMENTAL RESULTS Polycrystals. Tension and Compression Tcsls. It is apparent from Fig. 1(a) that above 170°K fracture of Molybdenum X takes place at stresses equal to or greater than the compressive yield stress whereas

Jan 1, 1967

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.&apos; At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By Gen-ichi Nakazawa, Masamichi Fujimori, Ichiro Doi

INTRODUCTION The major products of nickel industry in Japan are the electrolytic nickel (E-Ni), the ferro-nickel (Fe-Ni) and the nickel oxide sinter (NOS), totaling in production to 90 - 100 X 103 tons/year in terms of pure nickel content, and sharing approximately 20% for E-Ni, 10% or less for NOS, and the rest for Fe-Ni. The raw materials to be used for these products depend totally upon the imports from abroad; matte, the raw material used in the production of E-Ni, is from Australia and Indonesia; matte for the NOS is from Indonesia and New Caledonia; and garnierite, the raw material for Fe-Ni, is imported in bulk from New Caledonia, Indonesia and the Philippines. This report describes the acquisition of these raw materials, the production processes, trend of supply-demand, problem areas and the measures taken, and so forth, in connection with the nickel industry in Japan. ELECTROLYTIC NICKEL 1. History The nickel industry in Japan began in 1939 by the Sumitomo Metal Mining Co., Ltd. (SMM) with 150 tons E-Ni/month under the blast furnace smelting and the metal anode electrolysis. This was temporarily suspended after the end of last World War II, but resumed in 1952 with garnierite of New Caledonia as a raw material. Since then, the production capacity has been expanded incidentally to the increase of demand. However, since the smelting of garnierite contained about 2% nickel was very costly, the smelting process had been changed to smelt the briquettes of the mixture of garnierite and nickel sulfide concentrate imported from Canada and Australia. In 1975, this smelter was closed, and SMM&apos;s nickel refinery used matte from Western Mining Corp. (WMC) of Australia as a raw material. The refining process had been the metal anode one. The crude nickel oxide derived from roasting the high grade nickel matte had been melted and reduced with coke in the electric furnace and cast into anode. In 1970, a new refinery was constructed to produce 1,000 tons Ni/month under the matte anode process, and further, in 1976, the old refinery was converted into the matte anode process, thus resulting in the total production capacity of 1,690 tons Ni/ month today under the matte anode process. Shimura Kako Co., Ltd. began in 1951 to produce a little of E-Ni, and in 1955, they constructed a shaft furnace smelter with New Caledonian garnierite as a raw material to begin the E-Ni production under the matte anode process. Its monthly production reached 400 tons in 1957, but it discontinued its smeltering in 1963 to convert to the matte import from S. Le Nickel, WMC and INCO. In 1979, it changed the source of matte supply from the above to Soroako of Indonesia, discontinued the E-Ni production in 1979, and arranged for a total toll contract with Sumitomo. Meanwhile, SMM has developed a very distingished process for nickel-cobalt separation and refining by a solvent extraction method from nickel and cobalt mixed sulfide generated as a by-product in the nickel recovering process from laterite under the Nicaro process. Nippon Mining Co., Ltd. (NMC) also developed its own process. The plants under these processes were constructed in 1975, with the monthly production capacity of 230 tons of nickel and 130 tons of cobalt by SMM, and 300 tons of nickel and 110 tons of cobalt by NMC. SMM imports the raw material from the Marinduque Mining and Industrial Corp. of the Philippines, while NMC from Queensland Nickel Pty. Ltd. of Australia. 2. Production Status 2.1 Producers and materials Today, SMM holds the monthly E-Ni production capacity of 1,920 tons, of which 1,690 tons are from the matte anode process, and the remaining 230 tons are from the mixed sulfide as a raw material. NMC also uses the mixed sulfide as a raw material for a production of 300 tons/month. [ ] Most of SMM&apos;s raw material, nickel matte, is imported from WMC of Australia, partly using the Soroako matte from Indonesia. An example of material analysis is given in Table 1. Matte is a raw material for E-Ni and NOS, and the major sources of matte supply at present are Australian WMC and Indonesian Soroako, occupying ap-

Jan 1, 1982

By Leendert de Witte

Conventional resistivity logs consisting of a short normal, a long normal, and one or more long lateral curves do not give data that allow a complete quantitative interpretation in beds thinner than 20 ft. Reservoir rocks usually exhibit zones of continuous homogeneity of quite limited thickness where the long lateral curves become useless because of adjacent bed effects and boundary phenomena. If the beds are 12 ft or thicker, the short and long normals may be used for qualitative interpretation, which can be streamlined by the application of simplified departure curves. For beds of a thickness less than twice the long normal spacing, this procedure breaks down. The combination of the limestone curve, the later-olog or guard electrode log, and the microlaterolog permit quantitative interpretation for beds that are at least 10 ft thick, provided the mud resistivity and the hole diameter are known with sufficient accuracy. For beds thinner than 10 ft, combinations of the microlaterolog with short spaced laterologs and pseudo laterologs appear to be promising. Interpretation of these curves again requires the application of simplified departure curves. Resolution of various possible combinations was analyzed using departure curve data calculated on the Whirlwind I computer at the Massachusetts Institute of Technology. A field example is shown using the microlaterolog-microlog combination, and the combination of a 6-in. modified laterolog plus a 6-in. pseudo laterolog. INTRODUCTION For the purpose of quantitative interpretation of resistivity logs in porous formations, we want to obtain two essential quantities from the logs, namely, the true resistivity of the undisturbed formation, Rt, and the resistivity of the part of the formation invaded by mud filtrate, Rt. The apparent resistivities of all conventional logging devices are functions of these two parameters and are also influenced by a third unknown parameter, the diameter of the invaded zone, d. It has been shown&apos; that from the normal curves alone it is impossible to arrive at a unique solution for the three unknowns, Rt, R1, and d1. In very thick homogeneous beds, if invasion is not too deep, we can obtain a fair approximation to Rt from the long lateral curves and then use the two normal curves to find Rt and d1 Even under the most favorable conditions, the resolution of this system is not very good. The short normal does not give a reasonable approximation to R1 unless invasion is very deep (dl>16 hole diameters). For very deep invasion, however, the long laterals no longer approximate Rt. For bed thickness between 20 and 40 ft, the long laterals are affected appreciably by the adjacent beds; and the curves are distorted by boundary anomalies to the extent that they lose their quantitative usefulness in most cases. For the same bed thicknesses, the normal curves still function reasonably well. Although it is impossible to find unique solutions Lor R1 and Rt using the normal curves alone, we can obtain a reasonable approximation for the ratio R1/Rt through the use of simplified departure curves. This fact was brought to our attention by A. J. de Witte, geologist with Continental Oil Co. As the magnitude of Rl/Rt is a major clue to the presence of oil in formations, this method can be used to good advantage for qualitative analysis and will be discussed in somewhat greater detail. With the aid of suitable bed thickness corrections, the analysis of the normal curves may be used for bed thicknesses larger than 12 ft. For thinner beds, the method rapidly loses its resolution; and we have to resort to different types of resistivity logs if we want to attempt to analyze the curves quantitatively. The inadequacy of conventional resistivity curves in thin beds is far more serious than generally realized. Fig. 1 shows a conventional E. S. with a 16-in. and 64-in. normal and a 16-ft lateral through a section of Lansing-Kansas City lime, in comparison to a guard electrode survey through the same section in a neighboring well. The porous zones, which show up as low resistivity breaks on the guard electrode log, are completely masked by adjacent bed effects and boundary anomalies on the conventional curves. Even the short normal shows most of the porous Zones only as Vague deflections and in many cases fails to register Their

Jan 1, 1955

By Nicholas J. Grant, A. W. Mullendore

Measurements of grain boundary sliding were made on polycrystal and bicrystal tensile creep specimens of Al-2 pct Mg at 500oand 700oF. Grain and pain boundary orientation factors were studied with respect to their effect on the magnitude and direction of grain boundary sliding. It was concluded that a large part of the observed sliding may be caused by the operation of slip crossing the grain boundaries. Supporting evidence for this model from other investigations is also given. GRAIN boundary sliding in metals during elevated temperature deformation has frequently been thought of as an independent mechanism with its own characteristic stress, temperature, and structure dependence. Further, it is common to regard the grain boundary as the weak link during creep deformation since: 1) the strength of apolycrystallinemetal, as meas-sured by creep rate or rupture life, decreases at\a more rapid rate when sliding comes into action, and 2) grain boundary sliding, as revealed by "boundary darkening" and fold formation is often the first visible deformation. On the other hand, more quantitative observations, in both polycrystals and bicrystals, have shown boundary deformation to be closely related to the over-all deformation of the specimen. The curve of grain boundary contribution to elongation vs time takes a shape similar to that of the total creep curve,&apos;,&apos; and the apparent activation energy for sliding appears in most cases to have the same value as that for total creep.3 In order to reconcile these observations, one is left with these possibilities: 1) The grain boundary and grain deformation rates are both controlled by the same rate limiting processes. 2) The rate of sliding is limited by accommodation deformation in the grains. 3) Sliding is the consequence of grain deformation. 4) Grain deformation is dependent on prior grain boundary deformation. Alternatives 2) and 3) would view grain boundary sliding as occurring in series with another deformation process which could be rate controlling. McLean prefers item 3) as the sliding basis,4 where subgrain rotation results from dislocation accumulation in the substructure at the grain boundary. Crussard and Friedel&apos;s5 treatment of grain boundary migration considers that dislocations are forced into the grain boundary and are dissociated into dislocations with Burgers&apos; vectors nearly parallel to the grain boundary. The movement of these partial grain boundary dislocations then produces the sliding. The results of this investigation have indicated alternative 3) to be the most appropriate and it is this aspect of grain boundary sliding which will be analyzed. EXPERIMENTAL PROCEDURE Three types of tensile creep tests were employed in this study: (I) A constant load test of one very coarsegrained polycrystalline specimen at 500° F, 3600 psi, 1 pct per/hr strain rate to examine the grain and grain boundary orientation factors in grain boundary sliding. (II) Constant strain rate tests of polycrystalline specimens at 510o and 715o F, 2 pct per/hr strain rate to determine the grain boundary contribution to elongation at very low total strains. (m) Constant strain rate tests of bicrystals of various grain and grain boundary orientations at 500°F, 2 pct per/hr strain rate to obtain further information on the orientation effects in grain boundary sliding. The material used in the tests was a high-purity Al-1&apos;.92 mg alloy, kindly furnished by Alcoa. Its composition is given in Table I. The alloy is a solid solution at the test temperatures. The coarse grained polycrystalline specimen for test (I) was prepared by recrystallizingthe machined specimen, straining it about 1pct intension at room temperature and annealing at 900°F for 8hr. The constant strain rate specimens (11), with an 178 in. sq. by 1/2 in. long gage section, were cut from 1/8 in. thick sheet of cold rolled and annealed (8 hr at 1000oF) material. The latter specimens were supported in a special jig during the milling operations to avoid any bending, and the gage section was subsequently heavily electropolished to remove the cold-worked surface layer. The bicrystals (ID) were machined in the same

Jan 1, 1963

By A. E. Dwight

Lattice parameters were determined for eighteen equiatornic alloys of the CsCl-type structure, ten of which were previously un-reported. It was found that fomation of the CsCl-type structure in binary alloys of the transition elements is largely dependent on position of the elements in the periodic table. The relative size of the two elements was not found to be a controlling factor. A recent paper by Beck, Darby, and Arora1 corre-lates the occurrence of CsC1-type ordered structures with the position of the constituent elements in the periodic table for the first long period. It was also suggested that a definite increase in relative bond strength between unlike atoms occurred when, in binary alloys of iron-group elements, the other component is changed from a chromium-group element, to a vanadium-group element, to titanium. A later paper by Philip and Beck2 noted that the lattice contraction increased in the order CrFe, VFe, and TiFe. It was also noted by Philip and Beck2 that the lattice contractions of CsC1-type alloys decreased in the order: TiFe, TiCo, and TiNi, which is an apparent reversal of the contractions expected from the position in the periodic table. It was suggested that the increasing lattice contraction is an indication of increased stability, i.e., greater A-Bbond strength. The present investigation was carried out to determine whether the relation of the position in the periodic table to the formation of the CsC1-type structure was also correct for alloys involving the second and third long-period elements. A systematic search was made for CsC1-type structures among equiatomic alloys and for those found, the lattice contraction was determined. EXPERIMENTAL TECHNIQUE The elements Y, Gd, Ti, Zr, Hf, V, and Cb are designated the A group and the elements Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au are designated the B group. Equiatomic alloys were prepared for 57 AB combinations. The alloys were arc melted in a multicrucible furnace3 in buttons ranging from 5 to 20 g. Chemical analyses were not made, as the charge weights agreed closely with those of the buttons after melting. The alloy buttons were homogenized at 800° to 900°C. Metal log raphic and X-ray specimens were prepared and heat treated at temperatures from 600° to 1200°C. Specimens for X-ray diffraction were usually ground to a powder in an agate mortar; however, needle-shaped solid specimens were used when the alloy was sufficiently ductile to permit their preparation. Diffraction patterns were taken with a Straumanistype Debye-Scherrer camera using filtered Cu or Co radiation. The lattice parameters were obtained in A by plotting the calculated a0 values against the cos29/sin 0 + cos2?/? function and extrapolating linearly to ?= 900. Metallographic control specimens were polished on cloth wheels with diamond paste and etched with various phosphoric and nitric acid reagents. RESULTS The eighteen equiatomic alloys listed in Table I gave evidence of a cubic structure with two atoms in the unit cell, although two of these cubic structures exist only at elevated temperatures and transform to a tetragonal structure on quenching. Nine of these eighteen alloys gave diffraction patterns with super-lattice lines showing that the structure is of the CsC1-type. The lack of superlattice lines in patterns of the other nine alloys may be attributed to the small difference in atomic scattering power of the components. Metallographic study indicates the occurrence of nine narrow single-phase fields at the AB composition. Any or all of these nine may also have a CsC1-type structure. The VFe alloy was found to have a CsCl-type structure by Philip and Beck2 through the use of CrKa radiation (for which the scattering factor of V is anomalously low), whereas the Cu radiation used

Jan 1, 1960

By R. A. Greenkorn

This project originated in a practical problem—we needed five tracers that could be used together to locate flow paths in a pilot flood. While tracers for subsurface liquids have been used since the turn of the century,1-15 none of those reported in the literature appeared to be either consistent or quantitative enough for our purposes. Most were used in field systems without controlled experiments to determine the accuracy and precision of analysis, and many were tracers that could not be used collectively. The ideal tracer, of course, would follow the fiuid of interest exactly, traveling at the same velocity as the fluid front. But the ideal is impractical to attain because adsorption-desorption effects cause the tracer to lag behind the front; these effects, plus diffusion-dispersion effects, cause the tracer front to spread more than the fluid front. Thus, our objective was not to locate a tracer that would be ideal for all circumstances but rather, to find one that would approximately follow the fluid, or one that under controlled conditions could be corrected to calculate the movement of the fluid front. We considered tracers satisfactory—(1) if they were easy to analyze; (2) if their breakthrough-elution curves were not too different from those for the chloride ion, a tracer believed to follow the fluid front closely; and (3) if we could calculate from the curves a material balance, at 1.25-PV (pore volume) injected, within 5 per cent of that calculated from chloride curves. Of a possible 35 materials, we selected 13 tracers that could be quickly and easily identified and whose analysis was claimed to be accurate within 5 per cent. Only one of these, tritiated water, was a radioactive tracer. Radioactive tracers are easy to detect even in small quantities, but they require special handling and special equipment. Also, those that can be used together are limited because special equipment is required to separate emissions from the various tracers. Two of the original 13 tracers were eliminated in static tests to determine how accurately and precisely they could be analyzed, and to check on gross adsorption. The remaining 11 were flowed through a 9-ft linear sandstone model, and breakthrough-elution curves were obtained. Finally, three tracers were field-tested as breakthrough tracers. These tests are described in the following sections. The 13 tracers considered in these experiments were EDTA (ethylene diamine tetra acetic acid), fluo-rescein, picric acid, salicylic acid and ammonium, boron (as borate), bromide, dichromate, iodide, nitrate and thiocyanate ions, plus chloride ion and tritiated water. All but the chloride ion and tritiated water were subjected to static sand tests to eliminate the tracers that could not be analyzed quickly and accurately and to eliminate those that showed excessive adsorption. All but two of the tracers, EDTA and salicylic acid, qualified for flow tests on this basis. The procedures used in the static tests (see Appendix A for analytical details) were as follows. Each tracer (in the amount shown in Table 1) was dissolved in 1,000 ml of water. Then, 800 ml of this solution was added to 500 gm of sand, and the remaining 200 ml was reserved as a control standard. The sand-tracer mixture was agitated once a day over a 10-week period, and during this period we analyzed five duplicate samples from this mixture, along with five duplicate samples from the control solution. From the control-sample analyses, we constructed a control chart on which the sand-tracer analysis results were plotted. The control chart, and its use to determine accuracy and precision of analytical results, as well as the amount of adsorption, is described in Appendix B. The results of the static tests are summarized in Table 1, which lists the concentration c (concentration at time t) divided by c, (initial concentration). If there was no adsorption, c/c, = 1. The acceptable deviation from this value varied from tracer to tracer, depending upon the limits of analytical precision established for the different tracers. The best results were obtained with boron, bromide and dichromate, with all values falling within limits of accuracy and precision. Ammonium, iodide, nitrate and picric acid also were satisfactory, although the ammonium results were erratic. Flourescein and thiocyanate were unsatisfactory ini-

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.&apos; Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,&apos; and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-&apos; per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10&apos;* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965