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By K. D. Sheffler, R. W. Hertzberg, R. W. Kraft

The Ni-Ni,Ti lamellar eutectic alloy responds to unidirectional solidification by alig-nment of the platelets of the two phases roilghly perpendicular to the moving solid-liquid interface. X-ray diffraction and zetallographic experimenls show that the following cryslallographic relationships exist in the directionally solidified ingots: lamellar interface w [0001] Ni3Ti 11 (111 }Ni local growth direction (1120) Ni3Ti n (110) Ni These relationships are rationalized on the basis of the crystallography of the constituent phases. In recent years researchers in several laboratories have shown that an aligned or "controlled" micro-structure can be produced in many binary eutectic alloys by forcing the alloy to solidify unidirectionally in an elongated crucible.'-3 It also has been found that a unique crystallographic relationship often develops between the two phases in such a structure.4, 5 Since a parallel arrangement of phase particles in an alloy should, and, in many cases, does, produce unique and highly anisotropic properties, the alloys so produced are of potential interest in a variety of applications. Studies of these alloys are also of interest at the academic level because they help to improve our basic understanding of the way in which metals solidify. This paper reports the metallographic and crystallographic structure of another of these alloys—that between nickel and Ni3Ti. In a separate paper, hot tensile and stress rupture properties as well as deformation and fracture behavior of the same alloy are discussed.19 EXPERIMENTAL DETAILS AND RESULTS General Characteristics of the Eutectic Reaction. Several small exploratory Ni-Ti melts were made to resolve a conflict in Hansen6 over the eutectic composition. The alloy containing 16.4 at. pct Ti, Fig. 1, appeared metallographically to be closest to the eutectic composition, although small dendritic patches of proeutectic nickel are present. The eutectic morphology is lamellar and appears quite sharp and angular, indicating a strong influence of crystallographic factors upon the microstructure. Some of the eutectic nickel platelets are continuous with the primary phase, whereas in hyper eutectic melts a "halo" of nickel generally surrounded the proeutectic inter-metallic platelets, indicating that nickel is the nucleating phase in this eutectic reaction. Extensive precipitation of Ni3Ti has occurred in the primary nickel phase in a Widmanstatten pattern which makes the dendrites difficult to differentiate from the eutectic mixture. This phenomenon may account for discrepancies among the eutectic compositions reported in the literature. The sloping solvus line bounding the nickel primary solid solution explains the presence of the intermetallic precipitate. Poole and Hume-Rothery7 report that the solubility of titanium in nickel drops from 13.8 at. pct at the eutectic temperature (1304°C) to approximately 9 at. pct at 700°C (Ni3Ti, on the other hand, melts con-gruently and exhibits essentially no solubility for nickel or titanium). Lever rule calculations based upon Poole and Hume-Rothery's phase diagram indicate an increase from 21 vol pct Ni3Ti in the eutectic mixture at the eutectic temperature to 61 pct at room temperature. Selective point count measurements of the volume fraction of eutectic Ni3Ti platelets in the eutectic microstructure yielded a value of 46 i 2 vol pct, which required extensive precipitation of Ni3Ti from the nickel solid solution onto the eutectic intermetallic platelets during cooling from the solidification temperature. Influence of Directional Solidification. Nickel bar and titanium sponge of 99.9 pct purity were induction-melted in zirconia crucibles under argon in the proportion of 13.8 wt pct (16.4 at. pct) Ti to produce 14-lb master heats which were cast into investment molds yielding 5/8-in.-diam pins approximately 10 in. long. These pins were remelted under argon in horizontal zirconia boats and unidirectionally solidified to produce 1/2-in.-sq ingots approximately 44 in. long. Details of the experimental techniques and apparatus are described elsewhere.'

Jan 1, 1970

By Sidney A. Swensrud

MUCH discussion has occurred as to the use or uses which might be made after the war of either or both .of the large diameter (24 inch and 20 inch) War Emergency pipe lines built by y the United States Government during the war, to move crude petroleum and refined products such as gasoline and light distillate fuels. Indeed, the disposition and future use of these lines constitutes, in the minds of many people, one of the most important problems of postwar readjustment in the Oil Industry. The two lines, running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue normal ocean tanker movements from the Gulf Coast to the East Coast. Physically they could continue after the war to move crude or refined products, and it appears that lines of such large diameter as these, if operated at or near capacity, could move these liquids at costs per barrel which might be considered in the same general cost range as for tanker movements.1 If, therefore, we were to look forward at the end of the war to a shortage of tankers, it is probable that the continued use of these pipe lines for petroleum movements to the East Coast would be worth considering, as against building new tankers to take over the movement, provided there were no other economic or national defense reasons for restoring tanker fleets and no other better use for the pipe lines. Because of the extensive tanker construction program which has been and still is in progress, and because of our Navy's marked success in combating the submarine problem, it appears to be quite possible, however, that instead of a shortage of tankers at the end of the war, we may have a surplus instead. If this should turn out to be the case, then there would seem to be considerable doubt that these lines would continue to be used for moving petroleum or products to the East Coast at the expense of tying up tankers. It would hardly seem probable that the owner of any such tankers would ship via one of the large lines at the expense of tying up one of its own tankers, unless the pipe line tariff rate charged was lower than the out-of-pocket cost of operating a tanker as against the out-of-pocket cost of keeping it tied up. And considering that a substantial part of the cost of operating a tanker goes on even when it is tied up, it is very difficult to figure out how any pipeline tariff could be established that would be low enough to compete with individually owned tankers that otherwise would be idle. Certainly a pipe line tariff rate high enough to cover direct costs plus even a low rate of depreciation and return on the investment would be far above the out-of-pocket tanker operating costs. In view of these considerations, it has seemed desirable to examine with some care some of the various alternatives that have been suggested as to other possible uses to which these lines might be put. One of these is for transportation of natural gas to the New York-New Jersey Philadelphia area. This Eastern area, located at the destination of these lines, contains the heaviest concentration of population in the United States, and is not now served with natural gas. At the other end of the lines lie the greatest discovered natural gas reserves in the United States, if not in the world, and many

Jan 1, 1944

By Ralph W. M. Lai, D. W. Fuerstenau

This paper presents the results of a study of the principles which control the distribution of ultrafine particles between an oil phase and an aqueous phase. Alkyl sulfonates were used to control the wettability of fine alumina particles and to stabilize the water-isooctane emulsion system in the extraction process. The effects of sulfonate chain length, sulfonate adsorption, pH, and oil-water ratio on the recovery of solids in the oil phase were investigated. Higher extraction was found under conditions which yield higher hydrophobicity and large interfacial area of the oil-water emulsion. Today there is considerable interest in developing methods for the recovery of fine particles from disseminated ores. One such method might be the extraction of fine particulate solids from aqueous suspensions into an oil phase, and one example of a successful industrial process based on oil-water distribution phenomena is the emulsion flotation process used in concentrating manganese ore.' The oil agglomeration process of Farnand, Smith, and Puddington has been suggested for concentrating tin ore. Patents 3-4 for oil flotation processes extend back to that of William Haynes in 1860. The basis of all these processes is directly related to the stabilization of emulsions with solid particles. The first extensive study of oil-water emulsions stabilized by finely divided solids was made by Pickering. Later, Briggs,6 weston, 7 Chessman and King,8 and Leja and Schulman9 experimentally demonstrated how solid particles control water-oil and oil-water systems. Hildebrand10 suggested that fine particles can stabilize an emulsion because the fine particles are partially wettable by both oil and water, that is, that the contact angle must be finite. Takakuwa and Takamori 11 recently applied emulsion inversion to the study of collector adsorption in flotation systems. At the Royal School of Mines, Shergold and Mellgren12 are currently carrying out a comprehensive study of the extraction of fine particles into an organic liquid phase. In the present study of the liquid extraction or oil flotation of ultrafine particles, the recovery of hydro-philic alumina particles of 0.1-µ average diameter was determined after separating an isooctane-water mixture (emulsion) into its two phases. Alkyl sulfonates of different chain lengths were used to change the wettability of the alumina and to effect emulsifi-cation of the oil-water mixture. The effects of the oil-water volume ratio, sulfonate adsorption, and pH on the recovery of the fine particles were investigated. Since the surface charge on an oxide such as alumina is determined by the adsorption or interaction of H+ and OH- with the surface, pH control is extremely important. Furthermore, since the zero point of charge (zpc) of alumina13-14 occurs at pH 9 to 9.4, major adsorption effects with anionic collectors in these systems will occur below pH 9. The results of the foregoing investigation are discussed in terms of the recovery of the fine particles, the oil-water ratio, contact angles, surface tension, the adsorption of sulfonate onto the solid surface, and the emulsifica-tion of oil. MATERIALS AND EXPERIMENTAL METHODS Materials: The particulate solid used in all the experiments was Linde "A" alumina, a high-purity, readily available form of a-alumina. The surface area of the alumina, as evaluated from measurements of stearic acid adsorption from benzene, was 14.5 sq m per gm, based on a value of 20.5 sq Å for the cross-sectional area of stearic acid.13 All aqueous solutions were prepared from triply distilled conductivity water. Other materials included high-purity crystals of sodium alkyl sulfonates, isooctane, and, for pH adjustments, reagent grade hydrochloric acid and sodium hydroxide-Because sulfonic acids are strong acids, they are

Jan 1, 1969

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By E. F. Kingsbury

ONE of the well-known and important uses of the noble or precious metals has been for electrical contacts. In fact, the elements of this group, comprising gold, silver and the six platinum metals, have been called "noble" because of their ability to resist heat and corrosion, properties which were early found to be of importance in good contacts. Of these, platinum and its iridium alloys, palladium, and silver, have been extensively used. In recent years the electrical industry has been responsible for about one-eighth of the total consumption of the platinum metals in the United States. Information is not available as to what part of this one-eighth has been used for contacts but it is certainly an important one. SUBSTITUTES FOR PLATINUM During the past 20 years a considerable number of contact alloys have been proposed in the patent literature largely with the aim of more or less replacing platinum by gold or silver, and some of these alloys are finding increasingly widespread application as the reliability of their performance becomes established. From even the partial data-at hand it appears that this substitution by the less precious metals has replaced at least one-half of the amount of platinum that the entire electrical industry would otherwise be consuming at the present time. While the subject is of considerable interest to the metallurgist it is , even more so to the electrical engineer and it is surprising that the literature records no systematic and comprehensive investigation along these lines. Practically all the scattered work on noble metal contacts has centered around platinum as a Standard and has had two more or less distinct aims. One of these has been the replacement of platinum by cheaper materials, and the other, the development of materials of superior electrical performance. The merit of a contact metal has been assumed to be dependent on its infusibility, and since the more precious metals have the higher melting points there has naturally been an association of the two qualities in the sense that the more precious were

Jan 1, 1928

By A. M. Hall

SULPHUR, even in small amounts, may often be harmful to nickel and high-nickel alloys, causing impairment of mechanical strength and destruction of malleability and ductility, as shown by Merica and Waltenberg.1,2 It may act. either in the form of nonmetallic inclusions produced in the liquid state during furnacing or as reaction products resulting from its diffusion into the solid metal. In recognizing the action of this element, ability to identify its various forms by means of the microscope is often of considerable importance, especially when direct quantitative methods are inapplicable. [ ] Of the sulphur compounds associated with nickel and high-nickel alloys, the sulphides that may be found in malleable nickel, Monel? and Inconel? are an important group. These sulphides were investigated by metallographic methods in order to provide descriptive data by which to identify them. The nominal compositions of malleable nickel, Monet and Inconel are given in Table I. The term "sulphide" is employed here in a very general sense, to designate a substance in which sulphur and one or more metallic elements are combined. The term includes any combinations of compounds and solid solutions. METHOD OF INVESTIGATION Three groups of small laboratory melts were made, one group to represent each of the three types of alloy under investigation. Within each group, a number of ingots with a sufficient variety of chemical analyses were prepared so that the effect of each of the elements entering the complete commercial alloy could be isolated and observed. In most cases, to facilitate metallographic study by exaggerating the number and size of the resulting sulphides, somewhat greater amounts of the minor elements were added than are present in the commercial alloys. Likewise, considerably more sulphur was added than is normal, but not enough to complicate the system. Transverse sections were cut at a point one third of the distance from the butt to the head of each ingot, polished and examined with an inverted stage metallograph equipped with a combination polarizing-analyzing vertical illuminator. The light source was a tungsten-mercury vapor arc lamp.

Jan 1, 1943

By Oswald J. Heinrich

The deposit of rock salt along the shores of Lake Huron, in Canada, has been brought before the public during the last six months, in consequence of the developments made by the diamond drill at Goderich. It is likely to be of more than common interest in the future, since now actual operations have been commenced to exploit the deposit and work it by regular mining. The methods of mining rock salt being but little known in this country, it may be of interest to make a few general remarks in regard to them before entering, upon the description of this new mining enterprise. According to the conditions under which salt is .found in nature, various methods have been resorted to, in course of time, to make it available for the human race. They consist in: A. Natural or solar evaporation. B. Artificial evaporation, either exclusively or in connection with the former. C. Mining the rock salt in its natural state, and converting it to a marketable product, if need be, by simply pulverizing it. Without going into the details of the various methods of making salt available in an economical point of view, dependent on its degree of pority, or on various local influences, we cannot refrain from alluding to the general principles which influence the mining and manufacturing of salt in countries where they have been carried on for hundreds of years. ECONOMICAL CONDITIONS FOR SUCCESS. Salt being one of the articles of prime necessity, and one universally distributed throughout nature, it must always be sold at a comparatively low price. It would even be quoted in the market at prices far below those now ruling, if it were not for the high duties generally imposed upon it, for purposes of state revenues. But looking closer into the subject, it will be found that this duty is probably one of the least oppressive, although in some countries it exceeds sixfold the cost of profitable production. To produce the article at the lowest possible cost requires, therefore, a

Jan 1, 1879

By J. M. Donkers, R. de Groot

The various objectives of dredging at sea require different methods and radically different equipment for their optimum fulfillment. In the majority of cases, sea dredging is done by means of dredging equipment connected to a pontoon or ship floating at the surface. As the supporting hull is subject to the influence of waves, swells, currents and wind, the connecting point of the dredging equipment to the hull will generally move relative to the sea bottom with 6° of freedom. The more important hull motions are surge, heave, pitch and roll. Depending on the actual sea and weather conditions and the size of the hull, some of these motions can be so large that dredging equipment of rigid construction (normal or inland dredges) cannot be used. In those cases where mechanical disintegration of the bottom is necessary and where accurate dredging is required, the designer must find a solution for this problem. For cases where the bottom consists of soils that can be handled by plain suction, highly sophisticated dredging equipment such as the trailing suction hopper dredge permit dredging under all but the most severe sea state conditions. This type of dredge picks up the soil from the sea bottom while slowly underway. The drag suction head is fitted on a suction pipe of such flexibility that the supporting ship can carry out all six movements in relation to the draghead (heave, pitch, roll, sway, yaw and surge), while the draghead remains in firm contact with the bottom. The suction pipe is fitted with flexible hoses, a universal hinge, a horizontal hinge, axial turning gland and sliding turning gland with horizontal axis and is suspended flexibly from the ship incorporating swell compensating buffer gear, keeping the wires taut and the draghead bottom contact pressure fairly constant while the dredge moves up and down. Due to the fact that the draghead has a low bottom contact pressure and has little tendency to sink into the bottom, this compensation is not difficult to realize.

Jan 4, 1974

By E. P. Haqyes, J. K. Butler

011, and gas development has continued unabated on the Texas Gulf Coast during 1937. Although the number of important new discoveries has not been great, the extensions in older fields, owing to discovery of new sands and the lateral extension of known sands, has been extensive. Twenty-four new producing fields were added during the year, and many of these areas give promise of developing into important producing districts in the future. Alta Mesa, Amelia, Aransas, Clara Driscoll, Five Corners, Hamman, Heyser, Old Ocean, Premont, Seabreeae, Segno and West Columbia have all had major extensions during 1937. The 1937 production for the Texas Gulf Coast was 120,141,429 bbl., or 32f per cent increase over the 1936 production of 90,865,293 bb1. t The total number of producing wells has increased from 6727 to 8968. Well abandonments have becn few and indications are that they will continue to be so. Rigid proration has been and continues to be in effect, and, as a result, wells in the Gulf Coast will have prolonged life. New Fields Tables 1 and 2 contain general information on all fields in this district. The following named fields were discovered in 1937: Aransas County.—Barnsdall Oil Company's No. 1-A Edwards was the discovery well for the Lamar field. It was drilled to a total depth of 9785 ft., plugged back and completed at 7530 ft. in the Frio as a gas and distillate well. Present indications are not very promising for a major field. Bee County.—The McMurray (Strauch) field was discovered by Dirks Bros. No. 1 Strauch at a total depth of 4577 ft. This is a Yegua producer, and had an initial production of 230 bbl. on a 3/16-in. choke. Brazoria County.—The Sandy Point field was discovered by Henry DeArmanls No. 1 Fite, which was completed as a producer at 6501 ft. in the Marginulina-Frio series. Galveston County.—Although the Hitchcock field was discovered in 1936, the first commercial oil producer was completed in 1937 when

Jan 1, 1938

By C. H. Stewart, R. A. Fagin

A two-dimensional, three-phasereservoir simulator was programmed for a large memory digital computer. It was designed to provide a practical solution to describing the complex physical relation between the natural forces and the physical properties of a heterogeneous reservoir when subjected to a specific set of conditions. A reservoir study is briefly described to illustrate application of the model. A full volumetric account of three phases (oil, gas and water) is performed simultaneously throughout an integration net representing the reservoir. Absence of one or two of the phases is treated as a special case of the more general situation. Expansion (or contraction) of all phases, including rock expansion, is performed so that the pressure calculation is the general unsteady-state case. To account for the large variations of subsurface elevation encountered in some reseruoirs, and to allow for segregation of the various phases, a gravity head term is included in the basic drive potential. Appropriate fluid and rock properties are used in polynominal surface form (functions of pressure and/or depth) or they can be entered as space variables at each position of the integration net. An unsteady-state water influx calculation, based on the method of van Everdingen and Hurst, l was connected to the boundary of the matrix to simulate aquifers of various sizes. In addition to reservoir calculations, three-phase fluid flow from the producing depth to the wellhead, including provisions for gas lift, was incorporated in the simulator. A workover routine was also built which can automatically switch to a different set of production relations when a gas-oil ratio or water fraction reaches a limit; or it can shut-in the well if prescribed. INTRODUCTION This paper describes a reservoir engineering mathematical simulator used to represent the complex interaction of natural forces and physical properties of a reservoir during natural depletion or with various injection schemes. The simulator, which was programmed for a large memory digital computer, is a two-dimensional calculation which handles three mobile fluid phases simultaneously (oil, gas and water). Basic requisites for the method are individual well production and pressure data, hydrocarbon fluid properties, geological data (producing depth and net sand), capillary pressure data, relative permeability data and permeability and porosity information. Matching the past performance of a combination drive reservoir often has yielded information concerning continuity and the validity of basic data. Detailed predictions of future performance can be made for continuation of current depletion methods (natural depletion) as well as for various types of recovery by gas or water injection. Combination injection cases and pattern studies can also be performed. Workover programs, gas lift and different types of artificial lift programs have been investigated using a technique similar to that described by Kern and Nicholson2 except that conditions of pressure and saturation at the block within which the well is located are used rather than average reservoir conditions. Drilling additional wells to optimize profit was explored, both as to number and location, by placing wells at different spots within the reservoir matrix. Special depletion processes can be examined, such as upstructure drainage and lateral (or strike) waterfloods in thin oil columns. In one case the mathematics of the simulator were modified to calculate the displacement in the vertical plane rather than in the horizontal plane. In this manner specific reservoir problems can be studied, such as coning of gas and/or water around production points, fingering along permeable stringers or, more generally, frontal advances in a heterogeneous section.

Jan 1, 1967

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By C. A. Siebert, G. Sandoz

Oil quenching of steel, in good commercial practice, is carried out using a great deal of agitation in the quenching bath. Many of the tests reported in the literature represent the results obtained on steels quenched into still oil. Scott1 describes three stages of cooling in liquid quenching baths, namely: "State 'A'— Vapor Blanket Cooling—In this, the first stage, a thin stable vapor film surrounds the hot metal. Cooling is by conduction and radiation through the gaseous film and is therefore relatively slow. "Stage 'B'—Vapor Transport Cooling— Termination of the 'A' stage is marked by wetting of the metal surface. Vapor forms copiously in bubbles and is carried away by gravity and convection currents to condense in cooler surrounding liquid. This is the fastest stage of cooling. "Stage 'C'—Liquid Cooling—The 'B' stage ends as the surface temperature of the metal approaches the boiling point of the quenching liquid. Vapor no longer forms, so cooling is by conduction and convection and the temperature difference is greatly decreased. This mode of cooling is slower than that of the 'B' stage." Mechanical agitation of the quenching medium will accelerate all three stages of cooling. The greatest effect, however, will be noted on stage ' B' because the removal of the bubbles from the surface of the steel will not be entirely dependent upon gravity and natural convection currents. The method employed in this investigation for evaluating the oils was the end quench test. The various oils were substituted for water as the quenching liquid and hardness determinations were made at various distances from the quenched end. Most of the tests were run using a 3/8-in. orifice with a 21/2-in. stream height. However, to check the effect of other velocities two additional conditions were used, namely: (I) A 3/8-in. orifice and I-in. stream height, and (2) a 1/2-in. orifice and a 31/2-in. stream height. In all cases the samples were suspended so that the quenched end was 1/2-in. above the orifice. Some tests were run on an NE 8740, .3,312, and a 4340 steel. The results obtained on these steels confirmed those obtained on the NE 9450 and have therefore been Omitted from this paper. The test bars were machined from 1/8-in. stock to I-in. diam by 4 in. long.

Jan 1, 1949

By Wilford L. Stork

Certain influences of oxygen on iron have been known for many years and it has always been considered one of the worst enemies of the iron and steel founders. Nobody had a good word for it, hence little was done to make use of this oxygen. In all the fields of foundry practice, the desideratum was "melt without oxidation of the metal." In the consideration of the influence of oxygen on cast iron, we must not confuse this condition with oxidized iron caused by poor melting conditions, due to a high bed, heavy charges, low coke ratio, excessive melting rate, high blast, or poor charging. It is admitted that oxygen absorbed by iron melted under these conditions has a deleterious effect on the properties of the iron. The writer has had experience both in the melting under such poor conditions and in remedying these bad conditions and considers the product far inferior to iron melted under normal conditions. As stated by Dr. Richard Moldenke,l such iron has a higher melting point and high combined carbon, is sluggish, and contains slags and oxides in solution in the liquid, causing slag inclusions and gas occlusions, 'thus producing defective castings. This oxidized condition cannot be counteracted or removed by any of the known deoxidizers; it can be remedied only by proper melting conditions. Such iron is redly burned, whereas the iron considered in this paper was melted under normal conditions with moderate blast, correct bed height, light charges of iron, and low coke consumption and is not in this category at all. In 1914, the late J. E. Johnson, Jr., startled the metallurgists of the . world when he published his results on the advantages of oxygen on cast iron.2 His work is so convincing and so logical, in spite of the common and well-established notions on the subject, that nobody has been able to refute a single argument. Such an eminent authority on iron and steel metallurgy as Prof. H. M. Howe has accepted the work in all its details in his latest book.3 The work of J. E. Johnson, Jr., has revolutionized the metallurgy of cast iron and it seems apparent that all future work must include an oxygen determination just as we include silicon, sul-

Jan 1, 1920

By G. Sandoz, C. A. Siebert

Oil quenching of steel, in good commercial practice, is carried out using a great deal of agitation in the quenching bath. Many of the tests reported in the literature represent the results obtained on steels quenched into still oil. Scott1 describes three stages of cooling in liquid quenching baths, namely: "State 'A'— Vapor Blanket Cooling—In this, the first stage, a thin stable vapor film surrounds the hot metal. Cooling is by conduction and radiation through the gaseous film and is therefore relatively slow. "Stage 'B'—Vapor Transport Cooling— Termination of the 'A' stage is marked by wetting of the metal surface. Vapor forms copiously in bubbles and is carried away by gravity and convection currents to condense in cooler surrounding liquid. This is the fastest stage of cooling. "Stage 'C'—Liquid Cooling—The 'B' stage ends as the surface temperature of the metal approaches the boiling point of the quenching liquid. Vapor no longer forms, so cooling is by conduction and convection and the temperature difference is greatly decreased. This mode of cooling is slower than that of the 'B' stage." Mechanical agitation of the quenching medium will accelerate all three stages of cooling. The greatest effect, however, will be noted on stage ' B' because the removal of the bubbles from the surface of the steel will not be entirely dependent upon gravity and natural convection currents. The method employed in this investigation for evaluating the oils was the end quench test. The various oils were substituted for water as the quenching liquid and hardness determinations were made at various distances from the quenched end. Most of the tests were run using a 3/8-in. orifice with a 21/2-in. stream height. However, to check the effect of other velocities two additional conditions were used, namely: (I) A 3/8-in. orifice and I-in. stream height, and (2) a 1/2-in. orifice and a 31/2-in. stream height. In all cases the samples were suspended so that the quenched end was 1/2-in. above the orifice. Some tests were run on an NE 8740, .3,312, and a 4340 steel. The results obtained on these steels confirmed those obtained on the NE 9450 and have therefore been Omitted from this paper. The test bars were machined from 1/8-in. stock to I-in. diam by 4 in. long.

Jan 1, 1949

By H. H. Reamer, B. H. Sage

An experimental investigation was conducted upon five different paired samples of oil and gas from a field in Louisiana. The study, with each pair of samples, included the measurement of the formation volume and the volume of the liquid phase for three mixtures of the oil and gas. The gas-oil ratio varied from approximately 200 to over 40,000 cu ft per bbl and measurements were made at temperatures between 40" and 250°F. The gravity of the tank oil for the five samples under investigation varied between 38.0" and 55.8" API. The composition of the oil and gas samples and their mixtures is submitted 'References given at end of paper. Manuscript received at the office of the Petroleum Branch February 21, 1950. in tabular form. A number of diagrams depicting the effect of temperature and gas-oil ratio upon retrograde dew-point pressure are presented. INTRODUCTION During the past two decades a fairly large number of investigations were made of the volumetric behavior of naturally occurring hydrocarbon mixtures. The earlier work of Beecher and Park-hurst' and a more recent report on samples from Dominguez Field2 are typical of research of this nature. Such studies have been used in estimating the volumetric behavior of fluids in producing fields other than those from which samples were taken. Progress has been made3.4.5 in correlating the influence of pressure, temperature, and composition upon the specific and formation volume of hydrocarbon mixtures of relatively low gas-oil ratios, but attempts to extend this correlation to higher ratios have not been particularly successful. The influence of composition upon the volumetric behavior of such systems cannot be simply related to a single parameter such as gas-oil ratio. In order to aid in the extension of the correlation of the volumetric behavior of mixtures of oil and gas to higher ratios, a rather complete study was made of five different pairs of samples from a Louisiana field. The complexity of the influence of composition upon the volumetric and phase behavior of such systems in the regions of retrograde condensation was indicated by earlier Work,6,7,8,9,10 and it is doubtful if simple correlations can be established in these regions with the information currently available. The terminology employed in this paper is identical to that utilized earlier."

Jan 1, 1950

By T. L. Joseph

Sulfur balances calculated from operating data covering thirty-five blast furnaces indicate that approximately 92 per cent. of the total sulfur charged enters with the coke, 7 per cent. with the ore, and 1 per cent. with the stone.. Most of the sulfur is carried from the furnace by means of the slag, the total amount eliminated being the product of the slag volume and the percentage of sulfur it contains. Additional sulfur in the charge must be eliminated either by increasing the percentage of sulfur in the slag or the quantity of slag. From relations found between slag volume and coke consumption and sulfur in the coke and slag volume, curves have been prepared showing the relative value of blast-furnace coke as its sulfur varies from 1 per cent. CHARCOAL was the predominant blast-furnace fuel until 1838, when it was found, by the operation of a 2-ton experimental furnace, that anthracite could also be used. This information was a stimulus to the iron industry, particularly in eastern Pennsylvania where anthracite was available at low cost. The production of anthracite pig iron increased steadily and, in 1855, its tonnage exceeded that of charcoal iron. Of the 680 furnaces in operation in 1874, the 226 using anthracite produced nearly one-half the total tonnage. In 1869, the production of coke furnaces exceeded that of charcoal furnaces and, in 1875, coke surpassed anthracite as a metallurgical fuel. In 1907, the output of anthracite pig dropped well below a million tons and its present significance is largely historical. In recent years, the production of coke has gone hand in hand with the production of pig iron and it has gradually attained the position it now occupies as a universal blast-furnace fuel. Charcoal, however, has great merit as a blast-furnace fuel chiefly because of its freedom from ash and sulfur. The harmful effect of the latter and the necessity of keeping the percentage of this element in pig iron at a minimum are well recognized. Other contaminating elements can be reduced to specified limits in the steelmaking process, but the control of sulfur belongs essentially to the blast furnace. The purpose of this paper is to point out the distribution of this impurity in blast-furnace

Jan 9, 1924

By W. H. Kantner

IN this paper, no attempt will be made to theorize on subsidence. Only known data and actual facts will be given, with a few exceptions noted where other factors and outside influences tend to change sub-sidence directly resulting from porphyry caving. The area under observation is known as the Southeast Extension of the East orebody. The orebody is irregular in outline and dips to the south and the east, extending in depth from about 425 ft. below the sur-face to 1050 ft. below the surface. In the upper horizon, the orebody is about 400 ft. long and 150 ft. wide. At 720 ft. below the surface, the ore outline is approximately 450 by 170 ft.; 70 ft. below this, it is 500 by 110 ft., with an extension at the north end to the east 270 by 120 ft. From this elevation to about 900 ft. below the surface, the ore spreads out to the east and south, being about 700 by 500 ft. between these vertical limits. Below this it pinches out and at 1060 ft. below the surface is only 100 by 100 ft. The nearest point of the orebody-which is on the northwest side-is 600 ft. southeast of the Sacramento shaft. The country rock is all porphyry. Fig. 1 is a vertical east-west section showing orebody and original surface. The surface over the orebody was fairly regular and in this area and adjacent to it were portions of the surface plant, roads, and the main plant railroad to the concentrator. Fig. 2 is a map of the surface over the porphyry area. Caving operations started in April, 1925, at the approximate top of the orebody. The first lift was on the 600-ft. level; the ore was extracted by means of the Morenci timbered slide method and was from 425 to 455 ft. below the surface over an area of about 22,000 sq. ft. This lift was finished in May, 1926. The second lift, on the 650-ft. level, was already in production by May, 1926, so extraction of ore was continuous. This lift was 48 ft. high and covered an area of about 30,000 sq. ft. The ore from this lift was extracted by means of a modified Morenci timbered slide method. This lift was finished in March, 1927. The direction

Jan 1, 1934

By John T. Norton, V.G. Mooradian

The diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-torted lattice. On the other hand, it may be that the cold-working causes an increase in surface of contact between the two metals through fragmentation or provides a more intimate contact that is necessary for diffusion. If it is true that lattice distortion is an important factor in diffusion, it seems as if there should be some particular relation between

Jan 1, 1935

By V. G. Mooradian, John T. Norton

The diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-torted lattice. On the other hand, it may be that the cold-working causes an increase in surface of contact between the two metals through fragmentation or provides a more intimate contact that is necessary for diffusion. If it is true that lattice distortion is an important factor in diffusion, it seems as if there should be some particular relation between

Jan 1, 1935