Search Documents

By Ralph L. Erickson

The discovery of a Carlin-type gold deposit at Cortez, Nevada, in 1966 can be attributed directly to the use of geochemical exploration techniques. Most mineral deposits owe their discovery to geologic concepts, geologic analysis, and luck, but at Cortez, geochemistry as an exploration tool played the clearly dominant role in discovery. Of course, the economic significance of the discovery had to be determined by exploration and development drilling. The story of the discovery began in 1959 when field work was initiated on a new project, "Geochemical Halos Utah and Nevada," by R.L. Erickson and A. P. Marranzino for the US Geological Survey. The Cortez district was selected for geochemical work because it was an area with good geologic control where we could address the problem of how to prospect in barren outcrops for concealed ore deposits in potentially favorable structures (buried thrust zones) or favorable host rocks in the subsurface. Geologic mapping of the Cortez 15-min quadrangle, just being completed by Gilluly and Masursky (1965), showed that the quadrangle contained excellent exposures of both the upper and lower plates of the Roberts Mountains thrust fault, a major structural feature of north-central Nevada. Roberts (1960) had noted that a number of mining districts were associated with windows in the thrust. In 1959, Erickson and Marranzino did some reconnaissance rock sampling and spring-water sampling in the siliceous clastic rocks of the upper plate of the thrust. Results of this reconnaissance prompted a full-scale sampling program in 1960 in the upper plate rocks on the west flank of the Cortez window. Results of the investigation showed that anomalously high concentrations of metals occur in the upper plate rocks, and further, that the distribution of metals is fault controlled and shows a pronounced zoning pattern (central copper zone; intermediate zinc, copper, and lead zone; and outer arsenic zone). The anomalies were interpreted as primary leakage halos that originated from metal occurrences in the thrust zone or in carbonate rocks below the thrust and moved upward along normal faults that cut both upper and lower plate rocks. Erickson gave a talk about these anomalies in the summer of 1961 to the local AIME Section in Reno, Nevada; two short reports were published that year-" Geochemical Anomalies in the Upper Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1961) and "Hydrogeochemical Anomalies in Four Mile Canyon Near Cortez, Nevada" (Erickson and Marranzino, 1961). These releases prompted blanket staking in the area by several small companies. In 1963, geologic and geochemical mapping were started by the USGS in the lower plate carbonate rocks of the Cortez window west of the quartz monzonite stock at Mount Tenabo and north of the old townsite of Cortez. The results of the work showed anomalously high concentrations of arsenic, antimony, and tungsten in jasperoid, fracture filling, and shear zones in Silurian and Devonian carbonate rocks. The anomalous area was about 1.6 km (I mile) long and 300 m (1000 ft) wide. A brief report, "Geochemical Anomalies in the Lower Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1964a), was published in 1964. During this same time period, 1959-1964, several exploration or mining companies were active in the general area (chiefly mapping geology and acquiring property). In 1964, American Exploration and Mining Company (Amex) concluded that the entire Cortez district was worthy of an extensive exploration effort involving drilling as well as geologic, geophysical, and geochemical studies. To carry out the program, Amex formed a joint venture group with the Bunker Hill Company, Vernon Taylor, Jr., and Webb Resources. Their early efforts were directed to the upper plate rocks and to the lower levels of the old Cortez silver mine. The group also drilled some shallow rotary assessment holes adjacent to the area of the arsenic, antimony, tungsten anomaly in lower plate carbonate rocks described in Erickson et al. (1964a). Assay results from these holes offered little or no encouragement to the joint venture group. Splits of these drill samples were made available to the USGS. In order to enhance any metal content present in these rocks and to determine the mineral residence of any metals detected, heavy-mineral concentrates of each 3-m (10-ft) sam-

Jan 1, 1985

By A. R. Denison

Several productive areas in the Mid-Con-tinent are broadly and briefly examined with respect to the present depth of drilling on productive structures, and the thickness of sediments remaining untested. Evidence is offered to show that a vertical mile to two miles of untested but prospective formation remain within reach of the drill. In no case would a well deeper than 15,000 ft. be required, and in most cases to no greater depth than 10,000 ft. Recent outstanding success of deeper prospecting in West Texas demonstrates the merits of deeper drilling on known structure. Introduction New fields discoverd during I942 equaled or exceeded the number in any preceding year. The total amount of oil found by these discoveries was less than in any previous year, for which accurate records are available. This means that the pools now being discovered are much smaller than in past years. This is to be expected, since the prospects available during 1942 were largely those overlooked in the earlier years and therefore represent a second or third order (in quality) of structural feature. This failure to find pools of good size and quality raises grave doubt as to the security of our future oil supply. With military needs rising almost daily, and the period of heaviest con- sumption in our war effort still in the future, there is even a growing doubt as to our ability to supply the amount needed for our ultimate victory. This does not mean that our reserves are inadequate, but rather that our "capacity to produce" may be inadequate. Lacking large fields with flush production, our capacity to produce is rapidly approaching our current needs. ,Since the industry is unable to find the large new fields necessary to keep a safe margin of "capacity to produce," other means are needed. It seems obvious that one of these should be deeper prospecting on the large, proven, productive structural features now known. The exploratory wildcat is drilled primarily in search of a trap and the reason for failure to find oil and gas in nine out of ten cases is due to the absence of a suitable trap under the drill site. Therefore, deeper drilling on a known structural feature that is productive largely eliminates the greatest hazard in wildcat drilling. While by no means all the oil known today is found in structural traps—in fact, some have estimated that less than half is so located— the fact remains that structural traps are far more commonly the oil fields that have multiple horizons of production superimposed one over the other. Outstanding examples are the Eldorado field in Kansas, the Tonkawa and Cushing fields in Oklahoma, the Louden and Salem pools of Illinois, and the richest and most prolific of all structural traps, the Long Beach, Ven-tura and other similar fields of California.

Jan 1, 1944

By A. R. Denison

Several productive areas in the Mid-Con-tinent are broadly and briefly examined with respect to the present depth of drilling on productive structures, and the thickness of sediments remaining untested. Evidence is offered to show that a vertical mile to two miles of untested but prospective formation remain within reach of the drill. In no case would a well deeper than 15,000 ft. be required, and in most cases to no greater depth than 10,000 ft. Recent outstanding success of deeper prospecting in West Texas demonstrates the merits of deeper drilling on known structure. Introduction New fields discoverd during I942 equaled or exceeded the number in any preceding year. The total amount of oil found by these discoveries was less than in any previous year, for which accurate records are available. This means that the pools now being discovered are much smaller than in past years. This is to be expected, since the prospects available during 1942 were largely those overlooked in the earlier years and therefore represent a second or third order (in quality) of structural feature. This failure to find pools of good size and quality raises grave doubt as to the security of our future oil supply. With military needs rising almost daily, and the period of heaviest con- sumption in our war effort still in the future, there is even a growing doubt as to our ability to supply the amount needed for our ultimate victory. This does not mean that our reserves are inadequate, but rather that our "capacity to produce" may be inadequate. Lacking large fields with flush production, our capacity to produce is rapidly approaching our current needs. ,Since the industry is unable to find the large new fields necessary to keep a safe margin of "capacity to produce," other means are needed. It seems obvious that one of these should be deeper prospecting on the large, proven, productive structural features now known. The exploratory wildcat is drilled primarily in search of a trap and the reason for failure to find oil and gas in nine out of ten cases is due to the absence of a suitable trap under the drill site. Therefore, deeper drilling on a known structural feature that is productive largely eliminates the greatest hazard in wildcat drilling. While by no means all the oil known today is found in structural traps—in fact, some have estimated that less than half is so located— the fact remains that structural traps are far more commonly the oil fields that have multiple horizons of production superimposed one over the other. Outstanding examples are the Eldorado field in Kansas, the Tonkawa and Cushing fields in Oklahoma, the Louden and Salem pools of Illinois, and the richest and most prolific of all structural traps, the Long Beach, Ven-tura and other similar fields of California.

Jan 1, 1944

By C. H. Herty

Almost every metallurgist who has given the Howe Memorial Lecture has had a personal contact with the distinguished gentleman to whose honor this hour is devoted. Unfortunately for me, such personal contacts were not possible. However, in the preparation of a thesis on the open-hearth process, one of my earliest tasks was to make a survey of the literature, and it was from Professor Howe's Metallurgy of Iron and Steel that I drew a number of references to previous work which formed the foundation for my reading. In his volume there is such a complete exposition of the then current thought on the subject of slags and on their role in the elimination of phosphorus from steel that I feel no hesitation in discussing in this Howe Lecture the subject of "Slag Control." In the present era of close specification, the drive for uniformity of product, and the close inspection of the product and of the cost sheet, the utmost efforts must be made to control the steelmaking variables to the best advantage of the steel producer. One of the major variables is the slag in the furnace and its effect upon the composition and quality of the metal. What advantages are to be gained from slag control? In the broad sense the advantages must be tremendous, because the very foundations of good steel melting are based on "shaping up" the slag to a point where, with proper temperature, the heat is ready for the final additions. Every melter works toward these ends through his experience with innumerable heats of steel. The elimination of undesirable constituents such as phosphorus and sulphur is entirely a matter of slag composition and physical nature, a point well known for over half a century. The role played by the slag in assisting in proper heat transfer from roof and flame to the steel has been equally well known. In more recent years there has come the problem of oxygen control in the more accurate gauging of additions for making high-grade rimmed steel for the new strip mills, and in the deoxidizing additions for grain-size control and cleanliness of forging steels, both carbon and alloy. In this problem the oxidizing characteristics of the slag are of prime importance.

Jan 1, 1940

By C. H. Herty

Almost every metallurgist who has given the Howe Memorial Lecture has had a personal contact with the distinguished gentleman to whose honor this hour is devoted. Unfortunately for me, such personal contacts were not possible. However, in the preparation of a thesis on the open-hearth process, one of my earliest tasks was to make a survey of the literature, and it was from Professor Howe's Metallurgy of Iron and Steel that I drew a number of references to previous work which formed the foundation for my reading. In his volume there is such a complete exposition of the then current thought on the subject of slags and on their role in the elimination of phosphorus from steel that I feel no hesitation in discussing in this Howe Lecture the subject of "Slag Control." In the present era of close specification, the drive for uniformity of product, and the close inspection of the product and of the cost sheet, the utmost efforts must be made to control the steelmaking variables to the best advantage of the steel producer. One of the major variables is the slag in the furnace and its effect upon the composition and quality of the metal. What advantages are to be gained from slag control? In the broad sense the advantages must be tremendous, because the very foundations of good steel melting are based on "shaping up" the slag to a point where, with proper temperature, the heat is ready for the final additions. Every melter works toward these ends through his experience with innumerable heats of steel. The elimination of undesirable constituents such as phosphorus and sulphur is entirely a matter of slag composition and physical nature, a point well known for over half a century. The role played by the slag in assisting in proper heat transfer from roof and flame to the steel has been equally well known. In more recent years there has come the problem of oxygen control in the more accurate gauging of additions for making high-grade rimmed steel for the new strip mills, and in the deoxidizing additions for grain-size control and cleanliness of forging steels, both carbon and alloy. In this problem the oxidizing characteristics of the slag are of prime importance.

Jan 1, 1940

By C. E. Siebenthal

produce attractive and consequently more salable products. It would seem, however, that if solder and babbitt were cast in closed molds, just as good practical results would be obtained by the user, without his being able to give preference to solders of unnecessarily higher grade on account of their appearance. It would be hopeless for any one. manufacturer of solder to undertake a change of this kind, but if all manufacturers of solder agreed upon it, they would be able, in my opinion, to get the users of solder to take, and to approve by their practical tests, metals containing less tin than they have been accustomed to. The same is true with regard to babbitt metals. An illustration of how, in the use of an alloy, appearance sometimes is deceptive, is to be found in the case of what may be called intermediate grades of babbitt. I am thoroughly convinced that high-tin or high-lead babbitts are better than those containing both lead and tin with relatively high percentages of each. A high-tin babbitt should not contain more than about 10 per cent. of lead, and a high-lead babbitt should not contain more than 10 per cent. of tin, unless the percentage of antimony can be correspondingly increased. The intermediate babbitts, such as those that contain from 30 to 70 per cent. of lead or tin, may give nice appearing castings that flow easily, but they have not the serviceability of the high-lead or high-tin babbitts. Their hardness diminishes very rapidly as the temperature rises, and they have a relatively low softening point due to the eutectic components present. The Cadmium Supply of the united States* C. E. Siebenthal, † Washington., D. C.—From being one of the most maligned of metals—a veritable bugaboo—cadmium has almost overnight become respectable, though its slender claim to respectability rests almost wholly on the possibility of its substitution for tin. Preliminary to any campaign for such substitution, particularly for enforced substitution, the possible supply of cadmium should be determined as closely as possible; for that reason the statistical inquiry of which this paper embodies the results was undertaken. Production Cadmium is marketed in two forms, as metallic cadmium, in sticks or bars, and as cadmium sulfide, the pigment. The metal has found its greatest field of use in this country as a component of an easily fusible alloy that is used in automatic fire extinguishers. The sulfide is used to some extent in paints but chiefly to give color and luster to glass and porcelain. The metal was first made in this country by the Grasselli Chemical

Jan 1, 1919

By T. V. Philip, R. E. Lenhart

When commercial silicon iron sheets of varying magnetic quality are isothermally annealed at high temperatures, extremely large grains develop in the material having good magnetic properties. These grains are of the (110) [001] orientation and are formed by secondary recrystallization. The primary driving force for this secondary recrystallization is grain boundary free energy. For the secondary grains, activation energies of 103 kcal per mole for nucleation, and of 75.5 kcal per mole for growth, were obtained. The activation energy for nucleation of the secondary grains is consistent with a model involving redistribution of a precipitate acting as the primary grain growth inhibitor. SINGLY oriented silicon iron sheet was first produced in 1935.1 The material as commercially produced today has a very highly developed preferred orientation or texture; up to 95 pct of the grains are crystallographically oriented with their (110) planes in the plane of the sheet and their [loo] directions parallel to the rolling direction. This texture, usually written as (110) [00l], is referred to as the "GOSS" or the "cube-on-edge" texture. Because the magnetic properties of this material are superior to those of the nonoriented sheets in the direction of rolling, the oriented silicon iron has acquired tremendous industrial importance especially in the manufacture of transformer cores and other electrical equipment. The commercially produced material is essentially an iron-silicon alloy containing about 3 1/4 pct Si with minor impurities totaling less than 0.15 pct. The silicon steel heat is melted in the open hearth or electric furnace. The ingots are hot rolled, with or without being slabbed, to strips of 0.100 to 0.080 in. thickness. They are then cold reduced to an intermediate thickness, recrystallized, cold reduced to final thickness, decarburized, and finally annealed at a high temperature. During this high-temperature anneal, extremely large grains with the cube-on-edge texture are produced in the sheet. Several papers have appeared in the literature2-10 relating to the production of the Goss-textured material. Most of these describe the textures produced on cold rolling and on subsequent annealing of single crystal or polycrystalline silicon iron. May and Turnbull11,12 have recently shown the necessity of a second-phase dispersed impurity in the material for the production of the Goss texture. However, none of these papers describes in detail the nucleation and growth kinetics of the (110) [001] grains during the final high-temperature anneal.* The present work, therefore, is an attempt to understand the nucleation and growth kinetics of the cube-on-edge grains in the silicon iron sheet during the final high-temperature anneal.

Jan 1, 1962

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894

Jan 1, 1923

Illinois is rightly known as containing the coal deposit of which the first record in the United States was made. Joliet and Marquette saw "charbon de terre" along the Illinois River in 1673;1 LaSalle saw "mines de charbon" along the same stream in 1679; and Hennepin reported having "found in Several Places Some Pit-Coal" in 1682.2 In 1687 Jontel, in writing of the Illinois River country said, "along the river are coal pits, the coal whereof has been try'd and found very good."3 J. Carver reported the northern parts of the Mississippi River valley, "containing lead, copper, iron, coals, etc." in 17664 evidently referring to the Illinois country. Croghan, in the same year, saw coal along the Wabash River, near the mouth of the Vermilion in Indiana, but not far from Danville. Capt. Philip Pittman in his journey up the Mississippi in 1770 reported that "great pieces of coal are constantly found on the sand-banks, from whence it may be concluded, that there are coal-mines on the upper parts of the Mississipppi."5 This coal could only have come from the Illinois or Big Muddy Rivers. Morse, in 1798, refers to great quantities of coal on the upper branches of "the Father of Waters," and "on the Illinois River is a coal mine, which extends for half a mile along the middle of its banks."6 While, undoubtedly, some coal was used locally in various places, no records have been left of it and the first definite one is that in 1809 William Boon shipped some coal from the Big Muddy River, in Jackson County, to New Orleans, which was the first coal exported from Illinois.1 There has been considerable discussion as to this first shipment, whether it was made in 1809, 1810 or 1812. The records of arrivals of: boats in New Orleans in those early years is specific as to date, name of craft and name of captain, but no mention is made of cargo carried. William Boon arrived

Jan 1, 1942

By William D. Klopp, Joseph R. Stephens

Chromium alloys were coated with silicon, alumi-nuw, and boron by pack cementation. None of these simple coatings provided adequate nitridation/oxida-tion protection for a Cr -0.17pct Y alloy substrate as shown by a substantial Increase in the ductile -brittle transition temperature after air exposure for 100 hr at 2100°F. Iron-modified silicide coatings afforded good protection, holding the transition temperature of air-exposed specimens to 350° F compared to 200° F for uncoated unexposed specimens and 800°F for un-coated exposed specimens. Additional attractive cant-binations of modi-tying elements included Fe-mo, Fe-Mo-W, Fe-,Mo-W-Ti, and V-Mo-W-Ti. THE desirability of increased operating tempera-tures as a mcans of improving the performance of ad-vanced air breathing engines has resulted in emphasis on the development of materials with high operating temperature capabilities. Chromium, because of its relatively low density (7.19 g per cu cm), high melt-ing point (3410°F), and adequate strength upon alloy-ing, is a candidate material for turbine buckets and stator vanes of advanced air breathing engines. How-even, chromium is not without severe limitations, the major one being susceptibility to nitrogen embrittle-ment upon exposure to air at high temperatures.1,2 For example, a 25-hr air exposure of a Cr-5 pct W* * All compositions in wt pct. alloy at 2100°F produces a 600°F increase in the duc-tile-brittle transition temperature.' Although dilute alloying with such elements as yttrium, lanthanum, arid thorium3,4 or strong nitride formers5 has been shown capable of reducing nitrogen embrittlement, it is apparent that some additional form of surface protection, such as coatings or claddings, will be required for long time service in air breathing engines. Studies of aluiminide6 and silicide7 coatings and of nickel-base claddingsl on chromium alloys to date have suggested that these protection systems are inadequate. Of the aluminidc systems Studied,6 a simple aluminum and an Fe-Al coating on a Cr-5 pct W-0.1 pct Y alloy showed the lowest air exposure weight gains. However, the air exposures raised the ductile-brittle transition temperature of the coated specimens to above 1600°F from an initial level in unexposed specimens of about 500°F. A second in-vestigation for protection of Cr-5 pct W-0.1 pct Y employed gas pressure bonded alloy foils as protective claddings.1 An aluminized Ni-20 pct Cr-20 pct W alloy plus an unalloyed tungsten barrier layer gave the best performance with air exposure lives based on appearance and weight gains of over 600 hr at 2100°F. However, the bend ductile-brittle transition tempera-ture was increased to at least 1000°F after 100 hr at

Jan 1, 1970

By A. L. Barnes

A number of reservoirs have been partially invaded by bottom water. Water flooding such reservoirs can be especially inefficient if the oil has a high viscosity because injected water will under-run the oil and emerge at producing wells without having displaced much oil. A possible means of improving water sweep efficiency would be to precede the water flood with a slug of water purposely thickened with a chemical additive. This possibility has been studied with a scaled laboratory flow model. The investigation was carried out on a model representing a 20-acre five-spot with one set of reservoir condition~. Displacements were performed with water, with viscous-water slugs of 10 and 25 per cent of the pore volume followed by water, and with all viscous water. Displacement tests were made at several rates of injection. For all cases, compared at the same producing water-oil ratio, an increase in rate resulted in an increase in volumetric sweep. The larger the quantity of viscous slug injected, the greater the crossflow of oil ahead of the displacing front and, thus, the lower the WOR during that period of a displacement. This investigation indicates that the injection of aqueous viscous slugs in this type of system would give some additional benefit over conventional flooding by (I) reducing the life of the flood, (2) reducing lifting costs and (3) increasing ultimate recovery. The benefits of a viscous-slug displacement would warrant its use if the viscous water could be created for a few cents per barrel. INTRODUCTION The most appropriate method for water flooding oil reservoirs which have been partially invaded by bottom water has been a problem of considerable interest. Such reservoirs, having good vertical permeability and unfavorable mobility ratios, are difficult to produce efficiently under normal waterflood procedures. Even though the injection wells have been plugged back above the oil-water contact and the water zone has been squeezed off, injection water will enter the formation and not only displace oil, but also much of it will displace the bottom water, thus creating a high producing water-oil ratio at the start of a flood (see Fig. 1). Since the rate of injection and the viscosity of the displacing fluid are the more easily controlled physical parameters of the reservoir, it is quite natural to study their effects on the volumetric sweep of the oil zone and on the producing water-oil ratio. Increasing the viscosity of the displacing fluid has two disadvantages—it reduces the maximum rate of injection into the reservoir, and it costs more than water. It was thought that the injection of a viscous-fluid slug, followed by water, would minimize these two disadvantages, increase the volumetric sweep of the oil zone and reduce the producing water-oil ratio. Water with an additive to increase viscosity would probably be the most effective. The primary purpose of this investigation was to determine the feasibility of injecting viscous-water slugs followed by water to improve or hasten oil recovery while reducing the producing water-oil ratios. The effect of injection rate upon recovery was also investigated. A laboratory model, scaled to a 20-acre five-spot prototype with one set of reservoir conditions, was constructed. Laboratory studies of displacements with (1) water, (2) viscous-water slugs of 10 and 25 per cent of the pore volume followed by water and (3) all viscous water were performed at several rates of injection. THEORY OF SAND MODEL SCALING There are two conventional means of determining scaling criteria. These are dimensional analysis and inspec-tional analysis. Determining scaling criteria by dimensional

By T. Toda, R. Maddin

A study has been made of the microstructure and mechanical properties of splat-cooled aluminum-base gold alloys with gold concentration from 0.25 to 5.0 wt pct. These alloys have been quenched from the liquid state by a torsion-catapult technique, which has made it possible to pepare specimens suitable for mechanical property measwements. From the electron micrographs it has been shown that the solid solubility of gold in aluminum can be extended to 2.5 wt pct (0.35 at. pct) by splat-cooling, while the maximum equilibrium solubility is known to be less than 0.3 wt pct (0.04 at. pct). The very fine grain size (several tenths of a micron), the extended solid solubility, and the fine dispersion of a second phase (AuAl2) contribute concurrently to a substantial strengthening effect. In Al-5 wt pct Au splat-cooled specimens of less than 50 thickness, the yield strength is 17 kg per sq mm or 6 times as large as the strength of bulk specimens. For the Al-1.0 to 2.5 wt pct Au solid solution obtained by splat-cooling, the yield strength reaches 7.5 kg per sq mm after an aging treatment (for 10 hr at 200°C), while it is 3.7 kg per sq mm for the corresponding bulk specimens. A great deal of research has been done in recent years on the structure and the properties of metals and alloys rapidly quenched from the liquid state.' The term "splat-cool" has been used with the meaning of a rapid quenching from the liquid state., The splat-cooling techniques have produced large numbers of new structures, which are expressed in terms of metastable phases,3 concentrated solid solutions,4 amorphous phases,5'6 new phases,7 and so forth. Nearly all previous studies have concentrated on the physical properties; i.e., crystallography, structure, electrical resistivity, magnetism, and so forth, of the splat-cooled metals and alloys. The mechanical strength of splat-cooled metals and alloys has hardly been investigated except for some recent work by MOSS' on A1-V alloys. The principle common to all experimental techniques developed to obtain very rapid quenching rates is based on the heat transfer by conduction. Liquid must be in good thermal contact with a substrate of high heat conductivity. Both of the published devices known as the "gun" and the "piston and anvil" techniques suffer from certain shortcomings. For example, the specimen obtained by the gun technique is very small and flaky, and hence inadequate for mechanical properties measurements. On the other hand if the material is forced to yield a continuous speci- men by the piston and anvil technique, it is probable that some plastic deformation occurs during the quench. A novel method for rapid quenching of a liquid metal or alloy, the "torsion-catapult", has been devised by Roberge and Herman9 at the University of Pennsylvania. In the apparatus the melt is thrown out of a curved furnace by a catapult and impinges on a copper substrate. The apparatus has the advantage of producing a continuous foil which is relatively large in size and of a quality suitable for the measurements of mechanical properties. The quenching rate is estimated to be of the order of l05 to l06 ºC per sec, (comparable to rates achieved by the piston and anvil technique). In selecting an alloy to be studied we were made aware of the fact that gold was believed to be "insoluble" in in and consequently age hardening in the A1-Au system appeared to be interesting. Quite recently Heirnendahl13-15 revealed that the solid solubility, as determined by transmission electron microscopy, was 0.3 wt pct Au at 640°C and 0.25 wt pct Au at 600°C, decreasing with decreasing temperature. In an A1-0.2 pct Au alloy after quenching from a solution treating temperature of 600°C the yield stress was 2 kg per sq mm, and it increased up to 6 kg per sq mm after aging for 1 to 10 hr at 200°C. The precipitation occurred in the form of platelike particles mainly on (100) matrix planes. The intermediate phase n', the equilibrium phase n (AuAl2), and lattice relationships between both precipitates and the matrix were also investigated by electron microscopy. One of the purposes of the present research is to determine whether or not the solid solubility in this system, in which gold has a very small solubility in

Jan 1, 1970

By Frederick Laist

ABOUT six years ago the Anaconda Copper Mining Co. decided to investigate the possibility of extracting zinc from the ores of certain mines in the Butte district. These ores are of a complex character and contain so much iron and lead that the concentrate contains only 33 to 35 per cent. zinc. Investigations showed that while a high-grade concentrate could not be obtained by ordinary methods, such as tabling and magnetic treatment, a fair grade could be made by the Horwood process. In this method, the concentrate resulting from the flotation of all of the sulfides is given a light roast and this calcine is subjected to flotation in the presence of a large amount of sulfuric acid; the resulting concentrate contains most of the zinc and a residue contains most of the iron. The fact that the lead, copper, and silver are divided approximately equally between the zinc concentrate and the iron residue and the large consumption of acid, which ranged from 50 to 100 lb. (22 to 45 kg.) per ton of concentrates, were serious objections to this plan. The zinc recovery, moreover, was low, as a considerable percentage invariably accompanied the iron. While a profit might be made on the ores by the use of this process, it was thought that other and more promising methods might be devised. After carefully studying the field and doing some laboratory work on various processes that had been suggested, it was decided that the electrolysis of sulfate solutions was the most promising. We soon found, as have other investigators, that the only way to obtain a good zinc deposit is to have the electrolyte free from all metals more electro-negative than zinc, such as copper, cadmium, lead, arsenic, antimony, etc. Arsenic and antimony are particularly injurious, causing very poor current efficiency and small yield per horsepower when present in amounts so small as almost to defy detection-1 mg. or less per liter.

Jan 10, 1920

By R. D. Reiswig

An increasing amount of high-temperature metall~?~gical research is carried out in resistively heated tube furnaces in which a bare specimen is suspended by a fine wire at the midpoint of the tube. It is shown that the assumption of near-blackbody conditions on the surface of the sample may give rise to errors in optical pyrometry of 50°C or more. A number of papers published in the metallurgical literature in recent years have described the use of high-temperature tube furnaces for heat treatments, melting-point determinations, and other work. Typically, the tube is of a refractory metal with open ends, is heated by the passage of an electric current, and has concentric cylindrical radiation shields outside it. In at least one of these,' the specimen is contained within a crucible having a small hole in its lid through which optical-pyrometer measurements are made under essentially blackbody conditions. In another design,* the specimen is inside a muffle which is concentric with the heater tube and which contains a number of washerlike longitudinal radi- ation shields to reduce axial temperature gradients and to give conditions near the specimen closer to those of a black cavity. Yet another design3 employs a wire specimen coaxial with the heater tube. Blackbody conditions are simulated by passing current from a separate supply through the wire until it "disappears" against the background (the inside of the heater tube) as seen through a radial spy hole in the tube. Good agreement with known melting points is achieved when an optical pyrometer is used under such disappearance conditions as the melting point is approached. That this latter method works so well is due, evidently, to considerations such as those mentioned by Dike4 and others.5-8 A more common method than the above, however, has been the suspension of an uncovered specimen by a fine wire in a resistively heated tube with open ends. A radial spy hole about midway between the ends of the tube permits optical-pyrometer observations on the specimen, the inside of the tube, or both. So observed, the specimen typically appears to differ but little in brightness temperature from the inside of the tube. According to De vos9 the radiation from such a spy hole in an empty tube of reasonable 1ength:diameter ratio (e.g., 10 or greater) should be essentially blackbody radiation. For these reasons, apparently, descriptions of work carried out in such furnaces usually include a statement to the effect that conditions surrounding

Jan 1, 1964

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir'e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5'11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard's method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970

By N. Standish

Heat transfer coefficients have been measured in beds of various packings irrigated with mercury and molten fusible alloy countercurrent to hot gases. The measured coefficients for both systems were found to increase with gas velocities and liquid rates. Correlations were determined which show this dependence and also indicate that heat transfer in these systems is influenced by the liquid flow characteristics and the thermal conductivity of the gas and the solid packings. A heat transfer model has beer2 proposed which explains the various features of the experimental results. On the basis of this study, which gives an insight into the heat exchange in the melting zone of the blast furnace, it was concluded that by comparison with the furnace stack heat transfer coefficients are about 1.5 times higher in the melting zone. EACH year large tonnages of metal are produced in operations which, in part, involve liquid metal irrigation of "packings" countercurrent to hot gases. The melting zone in blast furnaces and in cupolas is a good example of packings irrigated with a liquid melt countercurrent to gases. In all instances of this kind large amounts of heat are exchanged and it is desirable to have some knowledge of heat transfer phenomena involved in these systems. So far the most common method of analyzing furnace efficiencies, fuel requirements, and the general thermal state of the furnace has been through the use of heat balances. As heat balances are essentially statements of the first law of thermodynamics they give no real indication of the factors which govern heat transfer between phases in the various zones of blast furnaces. Hence, rational improvement in production efficiency and the development of theoretical models is only possible if the heat transfer characteristics are known at every stage of the process and related to the important variables involved. This has been generally recognized for some time but it was only recently that Kitaev et al.' have produced a comprehensive treatment of heat transfer in solid-gas countercurrent systems such as the blast furnace stack and the packed bed regenerator. Using their treatment it is now possible to predict the effect of particle size, thermal conductivity, bed porosity, and the flow rates of both the gas and the solid material on the heat transfer in the blast furnace stack. However, the stack of a blast furnace is only one part of an integral unit for which the heat transfer analysis cannot be complete without also considering the heat exchange in the melting zone. The complexity of heat transfer processes in this region of the furnace has so far escaped quantitative description. Yet, the melting zone accounts for a greater amount of heat exchange than all the other zones of the furnace put together. Moreover, if the reduction of oxides in the melting zone proceeds in part in the liquid state the importance of heat transfer on furnace productivity and on the metal and slag temperatures is obvious. THEORY Heat transfer for two-phase flow in packed beds is a complex problem involving a number of heat exchange paths for which interphase areas are not known with any degree of certainty. Analytical solution is, therefore, difficult. This difficulty is emphasized by noting that Rabinovich~ and Luck have only recently solved the steady-state heat transfer for simplified two-phase heat exchangers of known area. However, useful progress can be made for the system considered by making a not unreasonable assumption that the usual heat transfer considerations apply and restricting treatment to the steady state. For these conditions the rate of heat transfer dq in a height dz of a packed bed of unit area is: dq = UaATdz [I.] Integration of Eq. [I] then gives the total heat transferred: assuming both U, the overall heat transfer coefficient, and a, the interphase area, to be independent of bed height. Since a, in these systems, is unknown it is convenient to combine this term with U. The group U, then represents the overall heat transfer coefficient on a volumetric basis. If AT is linear with q, then for a bed of unit volume Eq. [Z] can be integrated to give: is the log mean of terminal temperature differences. From Eq. [3] U, can be readily calculated as q and {AT)im are experimentally obtained quantities, but a difficulty arises in interpreting its meaning. Two approaches are possible depending on whether the effect of packing in the transfer of heat is neglected or not. If the packing is thermally decoupled then the resistance concept gives the relationship: which states that the overall resistance is the sum of the gas phase and the liquid phase resistances (assuming areas are equal throughout). Because the resistance to heat transfer in liquid metals is negligible by comparison with that of the gas,4 Eq. [4] can be simplified, i.e.:

Jan 1, 1969

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.' The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962

By H. D. Outmans

In steady vertical flow, the interface of an immiscible liquid-liquid displacement is horizontal for any flow rate below the critical. In nonvertical flow, however, the shape of the interface in the steady state does depend on the flow rate, and the purpose of this paper is to calculate the unsteady interfaces during the transition of one steady state of flow to another. A knowledge of these transient interfaces is of considerable importance in reservoir engineering where the calculation of breakthrough recovery depends on the instant the interface reaches the producing wells and on the shape of the interface at that time. Although the emphasis is put on transient interlaces, which eventually approach stable equilibrium, it is shown that if the displacement exceeds a critical rate no equilibrium is possible. The interface is then unstable and viscous fingers are formed during the displacement. The critical rate and the shape of the transient and equilibrium interfaces are affected by the effective interfacial tension; but since this effective interfacial tension appears in the calculations only in combination with the inverse square of the thickness of the medium, its effect in the reservoir would appear to be negligible compared to its significance in model experiments. INTRODUCTION Stability criteria and the early growth of interfacial disturbances in a plane parallel to the boundaries of a dipping formation in which oil is displaced by an incompressible fluid were described in a previous paper.l This type of instability is significant in thin reservoirs. However, if the reservoir has appreciable thickness, then interfacial stability in vertical planes, normal to the upper and lower boundaries, also becomes important (the displacement is supposed to be parallel to these vertical planes). The difference between the two stability problems is that, in the first case, the intersections of the interface with planes parallel to the boundaries are normal to the direction of the displacement; in the second case, the intersections, this time with vertical planes, are not normal to the displacement. Instead, they are tilted at an angle which depends on the displacement rate. The tilt of steady interfaces was calculated by Dietz2 who also determined the critical rate of displacement for stability in the vertical plane by assuming that this rate would coincide with an interfacial tilt equal to the dip of the formation. The critical rate thus calculated is the same as has been found for thin reservoirs (see Eq. 1.1 of Ref. 1 and of the present paper). Dietz's calculation of the stable tilt was verified by laboratory experiments and the agreement was found to be fairly good.3 It is doubtful, however, that stable tilts actually exist in the reservoir because a change in production rate is not followed by an instantaneous adjustment of the interface to the new rate but, rather, by a transition period during which the interface changes from one equilibrium tilt to the other. The principal objective of this paper has been to describe these transient interfaces without putting any restrictions on the flow conditions or the shape of the interface, as had been done previously. The second objective was to compute the critical velocity, taking into account capillary effects, and the third was to evaluate, at least qualitatively, the shape of the front at rates above the critical, again without making the simplifying assumptions introduced by previous investigators.2,3 In the following sections two examples are given of the calculation of interfacial motion. The first describes this motion for an initially horizontal interface in a dipping layer, and the second for a vertical interface in a horizontal layer. The mathematical formulation of the problem is nonlinear in the boundary conditions, and this prohibits its solution in closed form. Instead, the solution is obtained in the form of higher-order approximations. 1 Before proceeding to a description of the mathematical model, however, we define two quantities