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By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by' flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (--CH2CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder[4] has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate-potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality.

Jan 1, 1952

By R. D. Nelson, F. E. Bowman

Assumptions are made of ideal mixing and that the density of silver can be obtained by extrapolating reported liquid density-temperature data through the freezing point back to the temperature range of interest. The results of this procedure using liquid silver density data of Kirshenbaum et al.5 are presented in Table I1 where it is observed that agreement is everywhere within <0.1 pct and generally is within 0.05 pct. Because the Sn-Ag alloys are dilute, the assumption of ideal behavior is, therefore, probably justified. In conclusion, the densities of dilute liquid solutions of silver in tin have been determined. Even for concentrations as low as 0.1 pct, the effect of silver on the density of liquid tin is clearly measurable. This work also suggests that for dilute alloys at temperatures far below the freezing point of the solute metal, densities may be accurately calculated by extrapolation of the pure metal data without having recourse to physical measurement on the alloy itself. plutonium having a grain size of about 100 µ. This paper presents data showing that large elongations of fine-grained a Pu can be obtained by using slow deformation rates. Large plasticity, however, of a Pu in compression has been observed.4 Reductions in thickness of 90 pct have been observed with no edge cracking. These large reductions are accompanied by concurrent re-crystallization. The deformation modes, which are quite complex, have been studied extensively by observing the deformation microstructures of polished surfaces that had been deformed in compression.5-7 Although slip apparently is a predominant mode of deformation at room temperature, grain boundary sliding and concurrent recrystallization become more predominant at high a temperatures.4&apos;7 Although recovery occurs,8,9 no grain growth has been reported in a Pu even at temperatures near the a =ß equilibrium temperature (-115oC), which is 0.7 of the calculated melting temperature of a Pu.10 From studies on other materials, it appears that high elongations can be obtained in alloys when the THE purpose of this technical note is to present briefly some data revealing high ductility of a Pu, which is normally considered brittle. The very low ductility of a Pu in tension has been reported by many investigators.&apos;-3 Gardner,1 for example, reported that the total elongation of a Pu at a testing speed of 0.015 ipm is less than 0.1 pct at room temperature and only about 1 pct at 100°C. The only tensile creep studies that have been reported&apos; indicate no large ductility, but they were performed on relatively low purity

Jan 1, 1970

The Alligator Ridge Project is owned jointly by Amselco Minerals Inc. and Occidental Minerals, with Amselco being the operator. It is the latest of Nevada&apos; s gold heap leaching operations , having gone into operation in October of 1980 after a design and construction period of only seven and one-half months. Alligator Ridge is located about 77 km (48 miles) northwest of Ely, Nevada. Three separate but adjacent ore bodies will be mined: Vantage I, II and III. The first lies virtually at the surface and is totally oxidized; the second is somewhat deeper and contains some carbonaceous material; and the third is at the lowest horizon and contains substantial carbonaceous ore. The ore is a Carlin- type siltstone which has been silicified, especially at depth, and contains finely disseminated free gold. Exploration drilling on Alligator Ridge resulted in the defining of an ore reserve of about 4.54 million mt (5 million st) averaging 4. 12 g Au per mt (0. 12 oz Au per st). A pilot heap leaching program was run during 1979. Because of the high content of fine material in portions of the ore body, one test heap of 5,000 tons was leached, after being crushed to 19 mm (314 in.), in the conventional manner using cyanide and caustic while a second heap of 2,500 tons of ore was agglomerated with cement before leaching. Results of this work were reported at the 1980 American Mining Congress meeting by Paul Chamberlin (see Bibliography). The test work clearly indicated the superior leaching qualities of the agglomerated ore, and the plant was designed on this basis. Run-of-mine ore is crushed in an open-air crushing plant using a jaw crusher followed by two cone crushers, one standard and one shorthead. Provision was made to bypass the shorthead when the ore is wet from rain or snow. Crushed ore at 19 mm (314 in.) size is mixed with cyanide solution and cement, with the ratio of the latter to the ore being 2 to 5 kg per mt (4 to 10 lb per st). The resulting moisture content is about 870, and the fines are effectively bound to the coarse particles so that migration of the fines in the heap does not take place during leaching. For agglomeration, Amselco uses a rotating drum 2. 75 m 0 by 6 m long (9 ft 6 by 20 ft). For the same agglomeration, Candelaria uses three "grasshopper" conveyors, with introduction of caustic- cyanide solution at the conveyor transfer points. Provision was made for future addition of cement slurry at these same points.

Jan 1, 1981

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"&apos; the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly 100 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson&apos;s X-ray data indicate that this decomposition is accompanied by a change in volume of as much as 5 per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson&apos; found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter5 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to 90 per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced 90 per cent when forged to ½ -in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By O. Katz, A. Spilners, M. Simnad

THE oxidation of titanium has been studied in recent years by a number of investigators.&apos;-W ne of the most important aspects of the reaction of titanium with oxygen, which has been observed by several of the investigators, is the extremely high solubility of oxygen in the metal. A detailed study of the Ti-0 systeml% as shown that the solubility limit of oxygen in a-titanium is approximately 14.5 wt pct 0 from 800" to 1700°C. The unusual oxidation behavior of titanium may be ascribed to this phenomenon, since part of the oxygen uptake enters into solid solution in the metal and only a part is available for scale formation. A more complete study of the kinetics of oxidation of titanium would require information on the influence of oxygen in solution in the metal upon the oxidation rate. Such information would also be of interest in regard to the theory of oxidation of metals. The authors have measured the oxidation rates of oxygen-saturated and oxygen-free titanium between 800" and 1200°C and have found appreciable differences in their rates of oxygen uptake and in the activation energies. The experimental set-up was similar to that described in a previous paper.u The course of oxida-dation was followed continously by attaching the specimen to a sensitive spring balance and observing the extension of the spring with time of oxidation. High purity electrolytic oxygen was used and precautions were taken to purify the gases employed. The specimens were prepared from iodide titanium and were ground on metallographic polishing papers to a fineness of 4/0. The furnace was first evacuated and filled with argon; the specimen was lowered into the furnace, which was then evacuated and filled with oxygen, after the specimen had reached the oxidation temperature in argon. The samples were presaturated with oxygen by means of the following procedure: Each specimen was first heated in oxygen at 1200°C until its increase in weight indicated 13.8 pct by weight uptake of oxygen. The furnace was then immediately evacuated and filled with purified argon five times. The specimen was heated in the argon atmosphere for a period of 72 hr at 1200°C in order to saturate the metal with oxygen by complete absorption of the scale. The temperature was lowered to the oxidation temperature, the furnace was evacuated and filled with oxygen, and the oxidation rate was followed by noting the extension of the spring balance. No oxide film was visible on these specimens at the start of the oxidation experiments. Titanium samples in the oxygen-free as-received condition were also oxidized and their oxidation rates measured. The results are shown in Figs. 1, 2, and 3, which indicate that the initial rates of uptake of oxygen by both the oxygen-saturated and oxygen-free specimens are parabolic at these temperatures. The rate of uptake of oxygen is, however, appreciably lower

Jan 1, 1956

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.&apos; 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. A. Wheeler

That lead and zinc deposits are the result of prolonged,, slow deposition is the idea of most students of ore deposits, and in many cases, where the ore-bearing solutions have been very weak or the precipitating conditions have been very feeble, the ore accumulations have undoubtedly taken a long period of time. As these two vital conditions have been subject to great variations in the different mining camps, the following example is highly interesting in showing that deposition can be very rapid under favorable conditions, geologically speaking, and also extremely recent. In fact, the writer is inclined to regard most, if not all, of the Mississippi Valley deposits of lead and zinc as probably being very young, at least not older than Tertiary, if not Quarternary, in age. The extensive Joplin lead and zinc district, in southwestern Missouri, which is about 60 years old and has numerous mines that were abandoned from 1 to 50 years ago, shows that the lead and zinc today are in an active condition of solution and redeposition, although these two metals occur in the predominant form of sulfides. The mine waters from the older and more or less abandoned portions of the district are frequently so acid, mainly from the oxidation of associated pyrite, as to necessitate the use of wooden pipes and pumps. The first boom in the Oklahoma zinc fields, which is the southwestern extension of the Joplin district, occurred when ore was accidentally struck in drilling a water well. Among the mines then opened up was the Mission mine, at Lincolnville, Ottawa County, Okla. This mine was opened in 1903 in lean "sheet ground," or a flat blanket formation of chert carrying disseminated zinc blende, or "jack," and galena. Theore-body was very free from iron pyrites and the concentrates were very high grade, the "mineral," or lead concentrates, assayed 80 to 85 per cent. lead and the jack, or sphalerite, assayed 60 to 65 per cent. zinc. The orebody was very shallow, occurring at a depth of 76 to 95 ft. (22 to 28 m.) and very wet, requiring three or four pumps to handle the water. The mine was operated until 1914, when it was closed by litigation and immediately filled with water. The second Oklahoma boom, five years ago, opened up the large, active camps of Picher, Tar River, and Century, which are located 2 to 5 mi. west of Lincolnville. They are considerably deeper, being farther down on the westwardly dipping monocline that emanates from the Ozark

Jan 1, 1920

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,&apos; but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,&apos; strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By A. H. Daane, B. J. Beaudry

The uranium-antimony system has been investigated by metal-lographic, therma1, and X-ray methods. There are four intermediate phases present: USbz and U,Sb, which undergo peritectic decomposition at 1355°and 1695OC, respectively, and USb and UPSbs which melt congruently at 1850"and 1800°C, respectively. There is a eutectic between U4Sbs and USb which melts at 1770°C. USb,, UsSb4, and USb are line compounds while U4Sbs has a solubility range of approximately 1.5 at. pct at 1770°C. Single crystal studies of the cmpo,und U.,SbS show it to have a hexagonal unit cell with a, = 9.268A and c, = 6.201b;. The solubility of uranium in liquid antimony increases from 0.1 at. pct at 650°C to 1.5 at. pct at 900°C. The solubility of antimony in a, P, and y uranium is approximately 0.02, 0.1, and 0.05 at. pct respectively. IN nuclear reactors, uranium has been used mainly in the form of solid-fuel elements of the pure-metal or uranium-rich alloys. However, in attempts to overcome some of the difficulties inherent in solid-fueled reactors, reactor concepts hive been proposed in which the fuel would be a liquid metal, such as a solution of uranium in another metal. The liquid-metal fueled reactor (LMFR) designed by the Brook-haven National Laboratory of the U.S. Atomic Energy Commission is an example. Fuel for this reactor is a solution of approximately 800 ppm enriched uranium in bismuth.&apos; To design such liquid-fueled reactors, a background of information on the solubility of uranium in various metals is obviously necessary. The present study was undertaken to pro- vide information for such purposes, and in addition, to study the uranium-antimony system as a whole. A preliminary literature search showed that some work had been done previously on uranium-antimony alloys, but no attempts had been made to make a complete study of this system. The solubility of uranium in antimony was studied by Cammack and Bridger&apos; up to 950°C and by Hayes and Gordon up to 900&apos;-C. Their data are plotted in Fig. 1. Ferro, in an X-ray structure study of some uranium-antimony compounds, found USg to be tetragonal with a, = 4.2724 and c, = 8.471A, U3S4 to be b.c.c. with aO = 9.095A and USb to be f.c.c. with a,= 6.191A. Colani reported the compound UsSba; however, work by Ferro and by this Laboratory showed that this compound does not exist. foote&apos; reported several intermediate phases in the uranium-antimony system, but did not identify them. Greninger&apos; re-ported finding an intermediate phase in a 5 at. pct Sb

Jan 1, 1960

The Candelaria deposit was first discovered by Spanish prospectors in 1863; but its silver ore was not exploited on a large scale until 1873, when the Northern Belle mine was opened. The first Northern Belle mill was built at Belleville, 13 km (8 miles) to the northwest. From 1876 to 1886 the Northern Belle paid over $1 million in dividends each year. In 1882 a 43 km (27 miles) pipeline was built to Candelaria from the White Mountains to the west to furnish water for the mills and town at Candelaria; it was 100 mm (4 in.) in diameter, hand- riveted, and made in England. Sections of this pipe are used. as claim posts today. At its terminus at Metallic City, above Candelaria, a large concrete reservoir was built and called Metallic Lake. It is being used today by Candelaria Partners. Production at Candelaria declined after the mid-1980s, revived for a short period in the early 1890s, and during the 1920s a 300 ton mill operated for three years. Candelaria Partners is owned jointly by Occidental Minerals and Congdon and Carey, with Occidental being the operator. An engineering study done in mid-1979 resulted in engineering for the plant commencing in late that year and heap leaching being started in September 1980. Two million tons of ore per year containing 108 g Ag and 0.28 g Au per mt (3.15 oz Ag and 0.008 oz Au per st) will be mined from the Lucky Hill and Mount Diablo .areas about 1.6 km (1 mile) up Pickhandle gulch from the heap leaching operation. Waste -to -ore ratio is about 2:l. Ore is mined by front-end loaders and hauled by 85 ton trucks to the primary crusher, a 1,070 by 1,780 mm (42 by 70 in. ) gyratory. Primary crushed ore is conveyed to a stockpile of 10,000 tons live capacity from which it is reclaimed by hydraulic reciprocating feeders and conveyed to the crushing and agglomeration facility. This unit is composed of a 1.8 m by 2.6. m (6 ft by 12 ft) double deck screen, a 2.1 m (7 ft) standard cone crusher, and three conveyors. At the conveyor transfer points NaOH and NaCN solution is sprayed on the ore as it falls through a row of 75 mm (3 in.) hanging steel bars. During this process of turning and dividing the ore, the fines agglomerate with the coarse ore to give better percolation for the leach solution on the heaps. Provision was made for the later addition of 2 kg per mt (4 lb per st) of cement to aid in the agglomeration. Agglomerated ore at minus 50 mm (2 in.) size is then conveyed to a 390 mt (430 st) loadout bin where it is transferred to 85 ton rear dump trucks for haulage to the leach pads.

Jan 1, 1981

By H. R. Ogden, A. G. Imgram, D. N. Williams

The effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. Increasing the chromium, vandium, or aluminum content increased the strength of quenched structures with chromium being the most effective strengthener. Appreciable aging response was obtained with low chromium alloys, but high chromium alloys age softened rather than. hardened. High vanadium contents had a similar effect. Aluminum additions shifted the aging behavior toward that observed in lower chromium alloys, enabling high chromium alloys to be age hardened. DURING the course of titanium alloy development many a and a-ß alloys have been evolved to commercial status. However, only one all-ß alloy has achieved this same stature. This is the Ti-13V-11Cr-3Al alloy. It is characterized by a very sluggish ß-phase decomposition reaction such that very slow cooling rates can retain the 0 phase at room temperature. In addition, very high strength levels can be obtained by long-time aging treatments. Combinations of cold or warm working followed by aging produce even further improvements in strength. This paper describes the results of a research program in which the effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. EXPERIMENTAL PROCEDURES Electrolytically refined, high-purity titanium was used as the alloy base for these studies. Iodide chromium, electrolytically refined vanadium granules, and high-purity aluminum sheet were used as alloying additions. The compositions of interest were melted as 250-g ingots in a direct current arc melting furnace under a flowing atmosphere of argon. The ingots were hot forged to 3/4-in.-diam bars, vacuum annealed for 6 hr at 1800°F to reduce residual hydrogen content, and then hot swaged to 1/4-in.-diam rods. Fabrication history, and interstitial analyses after fabrication are given in Table I. All specimens to be heat treated were sealed in Vycor capsules under a partial pressure of argon. Samples used to define the ß transus were quenched from temperatures ranging from 1350° to 1100°F after holding at temperature for 15 min. Samples for aging studies were quenched from above the ß transus temperature and then aged for up to 64 hr at 750°F and for 100 hr at 850°, 900°, and 950°F. The effects of straining prior to aging were also investigated. The results of these studies were used to select the heat treatments for the tensile specimen blanks. Heat treatments of the tensile specimens are described in Table 11. Alloys were aged after solution heat treatment or after solution heat treatment and cold swaging to 50 pct reduction in area. Standard 0.125-in.-diam tensile specimens were machined from the heat-treated blanks. All tensile tests were performed in a Baldwin-Southwark uni-

Jan 1, 1963

By C. C. Nathan

Data are resented on the physical properties of five waxes obtained from fields in Texas and Louisiana in which "parafin" troubles are being experienced. The crude parafin was fractionated into three components, voluble in cold acetone, soluble in boiling acetone, and insoluble in boiling acetone. The acetone insoluble fraction was found to consist essentially of straight chain parafin hydrocarbons in the molecular weight range 525 to 700. Solubilities of the purified high molecular weight parafins were determined in a number of solvents. It was found that in hydrocarbon solvents, including crude oil, solubilities could be calculated satisfactorily by use of ideal solubility relations. In chlorinated, and oxygenated solvents, large deviations from ideal behavior were observed. These deviations could be partially correlated with the internal pressure of the solvent. INTRODUCTION A problem encountered in many producing oil fields is that of "paraffin" deposition. The problem refers to the deposition of material from the crude oil onto tubing, pumping rods, flow lines, or other material contacted by the crude. This problem has been recognized for nearly a hundred years, and numerous investigations have been reported on its causes and prevention or alleviation. One of the more comprehensive of such investigations was published by Reistle1 in 1932. A few of the salient findings of his report are briefly as follows: The term "paraffin" as used to describe this problem refers to the deposit of carbonaceous material which is not soluble or dispersible by the crude oil under the conditions where deposition occurs. The "paraffin" normally consists of high molecular weight paraffin hydrocarbons, both straight chain and branched, resins and asphaltic materials of undetermined nature, occluded oil and water, and possibly sand. In consistency, the deposit may vary from a soft, sticky material, to one which is hard and brittle. Deposits are usually black, although lighter colors are sometimes observed. Under the conditions of temperature, pressure, and crude oil composition occurring in the underground reservoir, the paraffin is in suspension or solution in the crude. As the oil flows to the surface, there is generally a reduction of temperature, pressure, and the amount of dissolved gases contained in the oil. Reduction of temperature and gas break-out were shown by Reistle to be factors causing reduced solubility of the paraffin in the crude. Thus, as the crude containing paraffin rises to the surface and flows to storage tanks at atmospheric temperature, the solubility of the paraffin may be exceeded. Deposition will begin at the point in the system where the temperature of the system falls below its cloud point, and continue as long as there is a further drop in the solution power of the crude for the paraffin. The severity of the deposition as well as the location of the bulk of the deposition, i.e., in subsurface or surface equipment, will depend on the amount of paraffin originally in the crude, the manner in which pressure and temperature of the crude

Jan 1, 1956

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson&apos;s X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes&apos; involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes&apos; involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By F. C. Holden, R. D. Buchheit

In the course of studies made on the Ti-Cu alloy system,&apos; particles identified visually as TiH were encountered unexpectedly in a specimen of high-purity Ti-0.8Cu alloy. The particles did not appear immediately after preparation, but following-storage in a dessicator for several days. Since the alloy had been vacuum annealed to a low hydrogen concentration (19 ppm by vacuum-fusion analysis), the appearance of the TiH particles was suspected as a surface contamination effect. A specimen of a Ti-0.8Cu alloy had been annealed 2 hr at 790°C and water quenched, to produce the single-phase equiaxed a structure. The metallo-graphic sample was ground through 600X paper, rough-polished on a high-speed wheel with a mixture of alumina and chromic acid, awLhish-polished on a slow-speed wheel. Disturbed metal layers were removed from the final surface by alternately etching with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution and polishing on the slow-speed wheel with fine alumina. The final surface was swab-etched with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution, rinsed in tap water, and dried in a stream of filtered air. The micro-structure, shown in Fig. 1, was composed of equiaxed a grains without any trace of second phase. After storage in a dessicator for 3 days, the appearance of small particles in the structure became evident (see Fig. 2). After 7 days of storage, the particles were more distinct, and in some grains, began to appear as elongated particles. The specimen then was etched a second time (without repolishing) to produce the structure shown in Fig. 4. On the basis of micro- structural observation, the line markings were identified as TiH; attempts to obtain diffraction patterns from the surface for positive identification were not successful. That the structure is a surface effect was demonstrated by grinding with 240X paper to remove the surface layer. The surface then was ground, polished, and etched using the procedures described previously. The same observations were made: the freshly prepared surface was devoid of any second phase, whereas the particles again appeared after several days storage. The same effect has been observed in other a-stabilized titanium alloys, including a high-purity Ti-0.20 alloy containing only 16 ppm H by analysis. The effect has not yet been observed in unalloyed titanium, nor does its appearance appear to be consistent with any particular alloy system. From these observations, it is concluded that certain a-titanium alloys are susceptible to the formation of titanium hydride at the surface of metallo-graphic specimens. The hydrogen probably is diffused into the surface from a residual film of etchant decomposition products. Estimates of the hydrogen

Jan 1, 1961

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.&apos; Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer&apos;s3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y&apos; phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS&apos; showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson&apos;s X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942