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By L. L. Handy

The development of a theory for miscible liquid displacement requires evaluation of the variables which affect growth of the mixing zone between solvent and displaced oil. Factors which appear to be important are individual fluid viscosities, viscosity ratios, flood rate, fluid densities, flow characteristics of the porous medium and molecular diffusion coefficients of the fluid components. The primary purpose of this paper is to evaluate diffusion effects. Theoretical treatments to date have been limited to floods for which the viscosity ratio is one. Two principal theories have been proposed. Von Rosenberg adapted for porous media a theory derived for capillary tubes by G. Taylor.' ,' In this theory molecular diffusion perpendicular to the direction of flow is a primary factor in sharpening the flood front. Slow floods give sharper fronts for a given distance traveled than fast floods. An alternative theory considers miscible liquid displacement as a statistical problem.3,4,5 Diffusion is not an important factor in this theory, but it leads to the same general type of equation as von Rosenberg's. Both theories predict S-shaped concentration profiles with the same dependence on distance traveled. The statistical or "dispersion" theory predicts rate independence, however. To supplement rate studies a direct measurement of a diffusion effect would be helpful in evaluating which of the two proposed mechanisms best describes miscible liquid displacement for one-to-one viscosity ratio systems. No quantitative theory has been proposed for floods in which a low-viscosity fluid displaces a high-viscosity fluid. It might be anticipated, however, that the extensive fingering observed in floods with adverse viscosity ratios would increase opportunities for an exchange of components between displaced and displacing liquids by a diffusional process. Even if molecular diffusion were not an important mixing mechanism for one-to-one viscosity ratio systems, it could be significant in systems with adverse viscosity ratios. METHOD FOR EVALUATING DIFFUSIONAL MIXING In solvent flooding the displacing liquid can become mixed with the displaced liquid by a number of processes; in general, either mechanical or diffusional in character. To evaluate the contribution of diffusion, a method was sought that would distinguish diffusional mixing from mechanical mixing. Suppose two soluble tracers are added to the displacing liquid and that one tracer has a diffusion coefficient much greater than the other. Then, if diffusion is important during miscible liquid displacement and if diffusional transport is primarily transverse to the direction of flow, substances with high diffusion coefficients will have sharper concentration profiles than those with comparatively low molecular diffusion coefficients. In order to have material balance the profiles for the two tracers must intersect. For one-to-one viscosity ratios the intersection would occur at the 50 per cent concentration point. It is generally assumed that diffusion in the direction of flow is negligible. This assumption appears reasonable because flow velocities are ordinarily orders of magnitude greater than diffusional velocities. If this is not a valid assumption, however, the shapes of the fronts will be further degraded by longitudinal diffusion. The effects of rate and molecular diffusion coefficients are the opposite for longitudinal diffusion to those for lateral diffusion. Higher rates or lower diffusion coefficients would tend to give sharper fronts. The double tracer method offers several unique advantages in evaluating effect of molecular diffusion. First, the method gives a direct measure of the effect of diffusion on mixing zone size. Second, the effect of a difference in diffusion coefficients is determined from a single experiment. Comparison of several experiments at different rates is not required. Third, the method is applicable for any viscosity ratio. Fourth, the method is unaffected by density differences between the two fluids which might result in rate dependent gravity effects. EXPERIMENTAL PROCEDURE Suitable tracers are substances whose diffusion coefficients differ as widely as possible, but whose adsorptions on rock surfaces is negligible. The two tracers selected were methanol and sucrose in water solutions. The approximate diffusion coefficients for methanol and sucrose, as given in the International Critical Tables, are 1.3 X 10-5 and 0.3 X 10-5 m2/sec, respectively. Concentrations in the water solutions were 200 gm/liter of solution for both methanol and sucrose. These high

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin's kin's and Flood's ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell' in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin's concept14 Flood's approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a'CaO is given by: Cs= 3—: Xa'CaO at 1500°C

Jan 1, 1970

By Michael Tenenbaum, T. L. Joseph

In a previous investigation1 the authors studied the effect of pressure on the reduction of iron ores by hydrogen. With hydrogen as a reducing agent, the rate of reduction was increased substantially by increasing the pressure from 1 to 2 atmospheres. The results with hydrogen prompted the present study of the effect of pressure on reduction with carbon monoxide and with mixtures of carbon monoxide and nitrogen. Features of Reduction Process The gas stream in the lower part of the blast furnace always contains sufficient concentrations of reducing gases to complete reduction provided sufficient time is allowed for the reaction to proceed. Reducing gases react immediately with the iron oxide on the surface of lumps of ore. However, as the unreduced surface recedes from the easily accessible exterior of the lump, the reaction proceeds by virtue of the diffusion of the gases into and out of individual pieces. The rate of diffusion of gases, which undoubtedly plays an important role in the reduction of iron ores, depends on several factors, most important of which are: (1) molecular weight or density, (2) pressure, (3) temperature, (4) concentration gradient. Thus, the rate of reduction of a lump of iron ore at any temperature will depend not only on the specific reaction rate but also upon: (1) available surface of unreduced iron oxide, (2) rate of diffusion of the reducing gas to the reacting surface, (3) rate of effusion of the gaseous products of the reaction from the reacting surface, (4) adsorption of the gases on the reacting surface. The various features of the reduction process were discussed in previous work and need not be reviewed. However, in order to explain

Jan 1, 1940

By Michael Tenenbaum, T. L. Joseph

In a previous investigation1 the authors studied the effect of pressure on the reduction of iron ores by hydrogen. With hydrogen as a reducing agent, the rate of reduction was increased substantially by increasing the pressure from 1 to 2 atmospheres. The results with hydrogen prompted the present study of the effect of pressure on reduction with carbon monoxide and with mixtures of carbon monoxide and nitrogen. Features of Reduction Process The gas stream in the lower part of the blast furnace always contains sufficient concentrations of reducing gases to complete reduction provided sufficient time is allowed for the reaction to proceed. Reducing gases react immediately with the iron oxide on the surface of lumps of ore. However, as the unreduced surface recedes from the easily accessible exterior of the lump, the reaction proceeds by virtue of the diffusion of the gases into and out of individual pieces. The rate of diffusion of gases, which undoubtedly plays an important role in the reduction of iron ores, depends on several factors, most important of which are: (1) molecular weight or density, (2) pressure, (3) temperature, (4) concentration gradient. Thus, the rate of reduction of a lump of iron ore at any temperature will depend not only on the specific reaction rate but also upon: (1) available surface of unreduced iron oxide, (2) rate of diffusion of the reducing gas to the reacting surface, (3) rate of effusion of the gaseous products of the reaction from the reacting surface, (4) adsorption of the gases on the reacting surface. The various features of the reduction process were discussed in previous work and need not be reviewed. However, in order to explain

Jan 1, 1940

By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets.1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741.3 Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name 'and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832.4 Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead," the zinc, and the rock or waste materials. The first record of zinc production from -the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons' in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with, considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1952

By R. J. Bethancourt, D. M. Collingwood

The use: of a pilot waterflood is very desirable where all of the pertinent data necessary to initiate a full scale waterflood are not. available. This paper attempts to take a specific case and .show the step by step process of starting with a pilot waterflood and progressing to a full wale flood as results are obtained. INTRODUCTION Many of the older fields of Soutlwest Texas are approaching depletion by primary produrtion methods. As primary protlllc:inp operations on individual properties approach their economic limit. conflicting considerations face management: cm the one hand. plugging and abandonment of wells for equipment salvage; on the other hand, further investment in secondary recovery installtions, equilent, and well workovers in the interests of conservation anal additional oil reserves. In main instances, where primary production by pressure depletion and gas solution drive has been comparatively good, there still exists the possibility of an economic secondary recovery by waterflood. This is not necessarily true to the same degrre of all such fields. nor all portions of large fields. To properly evaluate the economics of a prospective water-11ot1cI requires a considerable amount of precise geological. statitical. and physical data Such information on the older field.; is often very limited. and in the case of the property discussed in this paper was considered inadequate to justify investment in an overall waterflood. Primary production was estimated at :39 per cent of the original oil in place, yet sand conditions of permeability and homogeneity, and position in the field appeared to be favorable for a limited margin of profit from a carefully controlled waterflood. Thus a pilot waterflood, with its minimum initial financial risk, followed by extension as favorable results were obtained, seemed to be the answer for the Sun Oil Co L. Wiederkehr lease in the Nortl Government Wells Field, Duval County. Texas DESCRIPTION OF RESERVOIR Approxinately 8,200 wells have been drilled in Duval County. As of March 1, 1952, there were 3,350 producing oil wells in 92 different fields, with very few flowing wells (Fig. 1.) Sun Oil Co. operates the I.. Wiederkehr lease located in the North Government Wells Field in Duval Countv. 85 mile. west of Corpus Chriti and 100 miles south of San Antonio. The lease has been subjected in part to a controlled five spot waterflood. The North Government Wells Field is roughly 7 miles long and 3 miles wide, with numerous overlapping producing zones. The L. Wiederkehr lease of 3.085 acres. Has seven producing zones from 700 to 7.500 ft. The lease is in the northern section of the field where it is widest, and has 710 acres productive from the North Government Wells .and. (Fig. 2.) The North Government Wells sand, Jackson group. Eocene age, at an average depth of 2.250 ft (minus 1.750 subsea). has a thickness range of 25 ft on the east side of the L. Wiederkehr lease to 4 ft on the west side. It has a slight overall dip to the North and East of some 33 ft to the mile.

Jan 1, 1953

By C. W. Spencer, F. N. Rhines, R. J. Knight

Ametallographic study has been made of the peritectoid transformation as it occurs in two Ag-A1 alloys, containing 6.0 and 6.9 wt pct Al, respectively. After equilibrating at 475°C, these alloys were transformed isothermally just below the peritectoid temperature which lies at about 450°C.1-3 Peritectoid transformation in this alloy system consists in the reaction of a and 5 to form µ. The crystal structures of the a, µ, and 5 phases have been determined as face-centered-cubic, 6 manganese, and hexagonal-close-packed, respectively. At the peritectoid temperature their equilibrium compositions are approximately 5.85, 7.02, and 7.24 wt pct (19.92, 23.2, and 23.8 atomic pct) aluminum."" The transformation might be expected to occur principally at the interface between the a and 5, but such is not the case. Instead, the major part of the transformation occurs by the direct (and perhaps initially diffusionless) conversion of 5 to µ. The composition range of the forming µ nearly overlaps that of the parent at the temperature of transformation" so that little, if any, composition change is required. Transformation proceeds by the nucleation of µ at points upon the external surface of the sample and sweeps through the 5 phase, leaving the a initially almost undisturbed. Subsequently, the a phase participates in the transformation by being partly or totally converted to µ. Specimens approximately 1/4 x 1/4 x 1/16 in. were cut from cast ingots, previously equilibrated 68 hr at 588°C. The specimens were held for 3 hr at

Jan 1, 1958

By A. J. de Witte

INTRODUCTION The importance of determining dips of subsurface formations in wells, especially in wildcat wells, is self-evident and need not be enlarged upon. Various dipmeter instruments have been described in technical literature1,2,3,4 over the years. The introduction of the continuous dip-meters3,4 has made the earlier types obsolete. Continuous dipmeter logs are run by at least two different major service companies. Included as part of the service are a limited number of dip calculations—usually 10—made at different levels from the log. Very frequently this is the total result of a dip survey. It is believed that dipmeter surveys would be of considerably more advantage if geologists and engineers were able to make their own calculations from the original records. Determination of dips from the dipmeter record starts with the correlation of three log curves taken at different sides of the borehole. It cannot be over-emphasized that the quality of the results hinges primarily on this correlation. Nobody should be better qualified to correlate logs than a subsurface geologist or field engineer. The next requirement is to have an easy yet accurate way of computing the dip from the correlated points. Service companies use a mechanical device for this purpose. Directions for a graphical method were given in a recent article by B. 0. Prescotts. This paper describes a different graphical technique which, in our experience, is simpler, faster and at least as accurate. The entire manipulation is carried out on the stereonet in a number of easy moves. The paper is divided into two parts. This first part contains the introductory sections and full explanation of the geometry involved. The second part reviews the reading of data from an actual field log and summarizes the practical rules for computation of dips, the whole process being illustrated by an example. Following the outlined procedure, one could calculate a good many levels in a relatively short time, thus being able in particular to check suspected anomalies such as fault zones or unconformities in as close detail as the log will permit. GENERAL EXPOSITION OF THE METHOD Prnciple of the Dipmeter The position of a plane in space is defined by the location of three points, not on a straight line. Referring to Fig. I, if a borehole traverses a bedding plane, we can determine the strike and dip of the bed by finding three points which are not in line along this plane. Such points as A, B, and C are obtained with the dipmeter. The device consists of three electrodes (or caliper arms)1, 2, and 3 spaced at 120 angles, as schematically indicated, whose readings are separately recorded (Curves 1, 11, 111, to the right). When electrode 1 passes the boundary of the bed, Curve I will kick, etc. From these curves, we know the relative distances of points A, B, C, measured along the axis of the hole. If A is at zero, then B and C are at levels d1 and d2 up the hole,

Jan 1, 1957

By J. H. Bechtold, R. Kossowsky

1 HE superplastic behavior of the eutectoid A1-78 wt pct Zn alloy has been thoroughly investigated by Back-ofen et al.' The superplastic elongations and the marked resistance to necking were rationalized in terms of high strain rate sensitivity. In a subsequent paper2 superplastic behavior was formulated to show Nabarro-Herring diffusional creep as rate controlling at low strain rates, giving way to a dislocation climb process at higher strain rates. In a paper devoted to an interpretation of superplasticity in two-phase alloys, Packer and sherby3 have included the results of an examination of the structure of an Al-Zn eutectoid specimen before and after superplastic deformation. No significant change in grain size or directionality was observed in the deformed microstructures. This one observation led the authors3 to suggest that con- tinuous recrystallization or grain boundary migration was responsible for superplasticity. The purpose of this note is to report our observations on the superplastic behavior of the Al-Zn eutectoid alloy which differ in certain respects from works previously reported. Following Hayden et al., the results are discussed in terms of dislocation climb as the important factor during superplastic deformation. A heat of nominally high (99.995) purity 22 wt pct A1-78 wt pct Zn was induction-melted and cast into a 0.5 by 6 by 12 in. slab. The slab was heated to 350°C and rolled to 1/8-in.-thick plate. The plate was then cold-rolled to 0.040-in. thickness, annealed at 35OaC, and rolled to the final thickness of 0.020 in.* Speci-

Jan 1, 1969

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By John V. Beall

When a mine has ore averaging 5% lead, 7% zinc, 0.60% copper, 1/4 oz gold, and 6 oz of silver, adequate reserves, power and water, easy access to market, and is situated in beautiful natural surroundings with the advantages of a big city within a few hours drive, there is little left to be desired. Such a mine is the Mayflower mine of the New Park Mining Co. situated 30 miles from Salt Lake City in the Wasatch Mountains near Keetley, Utah.

Jan 1, 1949

By A. E. Deruyttere, J. Van der Planken, M. Laurent, Van den Bergen

FahRENHORST and schmid1 observed that zinc single crystals work hardened less rapidly when strained in liquid air (- 185°C)than in a bath at -82°C, whereas at higher temperatures the rate of work hardening decreased with increasing temperature, as would be expected. Cadmium and magnesium showed no such decrease at -185°C. At that time the observed anomaly for zinc at liquid air temperature probably seemed insignificant. However it later was confirmed2 by experiments in liquid nitrogen (-196°C) and in the mixture solid carbon dioxide-acetone (-77"C) and therefore appeared to be real. seeger3 then suggested that the anomaly might be due to the different wetting of the zinc crystals by the cooling media. Recently a new confirmation was obtained,4 however the cooling media again were different: the rate of strain hardening was found to be lower in liquid nitrogen and liquid oxygen than in pentane cooled to various temperatures down to -126°C. Ekperiments will now be reported in which the medium surrounding the specimen at the different temperatures was the same, namely gaseous air. The single crystals were made from "Overcor 99.99" zinc. They were grown in a vertical traveling furnace on seeds of nearly the same orientations. The diameter of the crystals was 5 mm and the length between shoulders 140 mm. The brass shoulders were stuck to the crystals by means of araldite. A thin steel wire was fixed to each shoulder and served to fasten the specimen to a Houns-field tensile testing machine. The crystals with the shoulders and part of the wires were surrounded by two concentric cylindrical containers. The coolant. either liquid air or ground solid carbon dioxide, was poured into the outer container only. During cooling the containers rested on a support which was removed when the straining was started. In order to check the temperature which the crystals would attain inside the inner container, a hollow bar of zinc in which a thermocouple was fitted was first mounted in the apparatus as a substitute for a crystal. It appeared that a constant temperature, respectively - 183° and -72°C, was attained inside the bar, if a soaking time of the order of 1 hr was allowed and if the outer container was constantly kept filled. Accordingly, this procedure was adopted for every tensile test. To take account of the large scatter, fourteen tensile tests were performed with liquid air and seven with solid carbon dioxide. The orientation of the crystals and the results are presented in the table, in which the symbols have the following meaning: 1 : temperature x : initial angle between basal plane and specimen axis : initial angle between slip direction and specimen axis a : shear strain at fracture 0: average rate of strain hardening = —-——- 100 t0 and Te representing respectively the critical shear stress and the shear stress at fracture. Despite the scatter of the a- and 8— values which is of the same order of magnitude as in the work reported by Seeger and Trzuble,4 it is evident that the strain hardening rate is significantly lower at -183°C thanat-72°C. The table also contains the average values calculated from Seeger and Trauble's results at the corresponding temperatures: z.e., four results at -183oC and two at-70°, -71°C. These authors calculated 9 in a slightly different way, but this is unimportant. The agreement between the a-values shows that both sets of experiments are comparable despite the differences in experimental techniques. The rates of strain hardening also agree and it may therefore be concluded that the anomaly is not

Jan 1, 1962

By J. L. Gregg

A study of copper-base and silver-base alloys was made with the object of finding, if possible, useful alloys subject to dispersion hardening. These studies led to the discovery of several alloys showing considerable dispersion hardening, the most important of which, the alloys of copper with iron, nickel, cobalt and chromium silicides, have since been very ably reported by M. G. Corson.l This paper is offered as a few notes covering alloys other than those described by Corson and some further data on the silicide alloys. Copper Alloys For the purpose of making a rapid survey of copper alloys that might show useful dispersion-hardening phenomena, various alloys were prepared containing 3 per cent. of additional elements added in such proportion that possible compounds could be formed without an excess of either added element. These alloys in the form of rolled or forged pieces were quenched in water from a temperature of 871" C. (1800" F.) and subsequently aged at various lower temperatures for l-hr. periods. The comparison of the Rockwell hardness of the quenched alloys with the maximum hardness of the alloys after aging was used as a measure of the dispersion hardening. Table 1 shows the Rockwell "E" hardness 1/8-in. ball, 100-kg. load) of the quenched alloys, together with the maximum hardness resulting from aging. The reheating temperature given in this table is the aging temperature at which maximum hardness resulted from a l-hr. sojourn. From this table it may be observed that only the silicide alloys showed significant dispersion hardening. Of these, the only one not described by Corson is the Cu-Be-Si alloy. This alloy contained 1.35 per cent. beryllium and 1.78 per cent. silicon, which is approximately equivalent to 3 per cent. Be2Si. It had a yellow color and scaled much less than the other silicide alloys upon heating. It could be worked easily either hot or cold but hardened very rapidly on cold working. The annealed alloy upon drawing from a diameter

Jan 1, 1929

By J. L. Gregg

A study of copper-base and silver-base alloys was made with the object of finding, if possible, useful alloys subject to dispersion hardening. These studies led to the discovery of several alloys showing considerable dispersion hardening, the most important of which, the alloys of copper with iron, nickel, cobalt and chromium silicides, have since been very ably reported by M. G. Corson.l This paper is offered as a few notes covering alloys other than those described by Corson and some further data on the silicide alloys. Copper Alloys For the purpose of making a rapid survey of copper alloys that might show useful dispersion-hardening phenomena, various alloys were prepared containing 3 per cent. of additional elements added in such proportion that possible compounds could be formed without an excess of either added element. These alloys in the form of rolled or forged pieces were quenched in water from a temperature of 871" C. (1800" F.) and subsequently aged at various lower temperatures for l-hr. periods. The comparison of the Rockwell hardness of the quenched alloys with the maximum hardness of the alloys after aging was used as a measure of the dispersion hardening. Table 1 shows the Rockwell "E" hardness 1/8-in. ball, 100-kg. load) of the quenched alloys, together with the maximum hardness resulting from aging. The reheating temperature given in this table is the aging temperature at which maximum hardness resulted from a l-hr. sojourn. From this table it may be observed that only the silicide alloys showed significant dispersion hardening. Of these, the only one not described by Corson is the Cu-Be-Si alloy. This alloy contained 1.35 per cent. beryllium and 1.78 per cent. silicon, which is approximately equivalent to 3 per cent. Be2Si. It had a yellow color and scaled much less than the other silicide alloys upon heating. It could be worked easily either hot or cold but hardened very rapidly on cold working. The annealed alloy upon drawing from a diameter

Jan 1, 1929

By T. A. Read, M. W. Burkart

The crystal geometry of the cubic-tetragonal interface after partial transformation of an indium-thallium alloy single crystal is described and a general theory is presented. The effects of applied stresses on this transformation are interpreted and the latent heat of transformation is obtained from observations of transformation under stress. A DIFFUSIONLESS phase transformation between face-centered cubic and face-centered tetragonal structures has been reported for the indium-thallium system by Bowles, Barrett, and Guttman1, 2 The transformation takes place at approximately 105 "C at 18 atomic pct Tl and 25°C at 23 pct Tl. In their study, Bowles, Barrett, and Guttman used poly-crystalline samples whereas in the present study single crystals were used to eliminate the transformation constraints imposed by adjoining grains. The use of single crystals made possible a comprehensive study of the effect of stress on the transformation. In the course of the work, it was possible to formulate a new method of analyzing dif-fusionless transformations (presented in this paper) which permits calculation of the geometry of the interphase interface from a knowledge of the crystal structures of the initial and final phases. The specimens were prepared from chemically pure thallium and 99.97 pct In which were weighed out to produce 3 to 4 grams of alloy of the desired concentration. The metal was placed in clean fused silica tubing, then melted, degassed and sealed under vacuum. (To obtain single crystals, it was found that both degassing and extreme cleanliness were essential.) Single-crystal specimens were grown by a modified Bridgman technique.8 pecimens were removed from the tube by dissolving the quartz in concentrated hydrofluoric acid which attacks the specimen very slowly. The specimen then was polished mechanically to produce four flat surfaces, electropolished, and annealed at 140°C for 48 hr. The electropolishing solution used was that described by Bowles, Barrett, and Guttman and the polishing was carried out on both the high and low temperature phases of the alloy. The high temperature polishing was done at 110°C with a stainless steel cathode. Visual Observation of the Transformation in Single Crystals A visual study of the transformation was made on specimens which had been electropolished in the high temperature phase. The specimens were supported on the stage of a metallograph by an electrically heated holder which contained an opening for observing the specimen. Visual evidence of transformation was found in the presence of an interface which separated the two phases. The interface plane defines the boundary of the phase undergoing transformation and manifests itself by the sharp change in angle between the surface of the specimen and the incident light at the juncture of the two phases. On slow cooling, well-annealed specimens transformed from the face-centered cubic structure to the face-centered tetragonal structure by the motion of a single plane interface which traversed the specimen from one end to the other. Upon heating, the interface moved back in the reverse direction. The interface could be started, stopped, or reversed at will. A temperature hysteresis of about 31/2oC was observed in the reversal of the interface. Holding an interface stationary caused it to disappear completely in most cases, whereas in other instances the interface became less distinct depending upon its orientation. The interface could be made to reappear by changing the temperature of the specimen. The low temperature tetragonal structure exhibits only the fine markings or subbands reported by Bowles, Barrett, and Guttman and is illustrated in Fig. 1. These subbands are twin-related. Back-reflection Laue patterns show the breakup of the cubic spots into pairs of spots corresponding to the twin orientations of the tetragonal phase.

Jan 1, 1954

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.' It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By E. L. Jr. Spain

THE deposits described in this paper occur over much of Wayne County and in the southeast portion of Hardin County, Tennessee, and in the northeast and northwest portions of. Mississippi and Alabama respec-tively. The presence of tripoli in this region has been known for some time and descriptions of various occurrences in Tennessee have been made by Jewell1 and Miser2, while Hilgard3, Lowe4 and Logan5 have treated the deposits that occur in the adjacent portions of Alabama and Mississippi, but there has not been a general survey of the entire field summarizing completely the geology of the deposits with respect to their origin and stratigraphic relationships. During 1934, while engaged in surveys of mineral resources through this region for the Tennessee Valley Authority, the writer collected data with this in mind, and has assembled them in this report. He is indebted to H. S. Rankin and N. A. Rose, of the Tennessee Valley Authority Geology Division, for field assistance.

Jan 1, 1936

R. B. BRINSMADE, Puebla, Puebla, Mexico (communication to the Secretary*) :-As I have previously considered the general equations for mine-valuation,1 I will here discuss only that part of Mr. Finlay's paper criticized by E. E. White, along with some of the general principles of mining taxation, under the following six topics: 1. Rate of interest earned by sinking-fund. 2. Rate of interest earned by investment. 3. Place of royalty item in valuation. 4. Place of taxation item in valuation. 5. Calculation of future ore-prices. 6. Valuation of undeveloped mining land. 1. Rate of Interest Earned by Sinking-Fund.-Mr. Denny's quoted opinion of a 3 per cent. rate is evidently based on English conditions before the Boer war. The great destruction of liquid capital by the great wars and catastrophes since 1897, along with the flood of gold and consequent rise in the average index of commodity prices, has undoubtedly increased the rate of interest at least one-half per cent. In the United States sound savings banks now allow 4 per cent. on deposits, while safe bonds are quoted at prices which yield even 5 per cent.. 2. Rate of interest Earned by Investment.-Gold-mines with uncertain and scanty ore reserves, the objects of Mr. Denny's quoted remarks, are quite different from iron,. copper, or coal mines with definite mineral reserves blocked out ahead by drilling or driving. While 10 per cent is often all inadequate yield from gold-mines, the latter class of mines are often, as safe as city real estate and resemble it as an investment in more ways than one.

Jan 10, 1913

By Walter C. Lawson

The first plans were made in 1930 for the mining by open-pit methods of the low-grade disseminated ore body now known as the Morenci open pit. It was not until 1937, however, that final plans were completed and the decision reached to go ahead with the actual development. Many advances were made in open-pit mining equipment during that period of seven years, therefore the ways and means of attack actually used were very different from those originally contemplated. Diesel-operated bulldozers, big trucks, full-revolving electric shovels and electric churn drills constitute the major equipment finally purchased for this modern stripping operation. Neither the bulldozers nor the big trucks were considered in the early operating plans, for at that time bulldozers had not been used in mining operations and the trucks as yet were undesigned. The full-revolving shovel and the churn drills were not new developments in open-pit equipment, but both had undergone remarkable manufacturing transition, emerging far more efficient and far more dependable than their predecessors. Even the ordinary drilling steel had been fundamentally changed. It was now threaded so that the dulled cutting bits could be detached and replaced, thus eliminating the costly transportation of long bars to the drill shop for resharpening. The decision to use trucks in the preliminary stripping operations was based on the desirability of this type of transportation to economically prepare the pit for rail haulage, coupled with the success that the contractors had had with them on other big excavation jobs. There are at present no plans for the use of trucks beyond the preliminary work, inasmuch as rail haulage will give lower costs after roadbeds and benches are once established. For many years to come, both ore and waste haulage will be over favorable grades. The average length of ore haul between the pit and an assembly yard will be about two miles. From there the crushers will be 1? miles with a connecting track grade of 0.4 per cent. The upper ore benches of the pit will be reached from the yard by a series of four switchbacks over a ruling grade of 4.0 per cent compensated for curvature. Tracks to the dumps will be on 0.2 per cent grades.

Jan 1, 1940

By Walter C. Lawson

The first plans were made in 1930 for the mining by open-pit methods of the low-grade disseminated ore body now known as the Morenci open pit. It was not until 1937, however, that final plans were completed and the decision reached to go ahead with the actual development. Many advances were made in open-pit mining equipment during that period of seven years, therefore the ways and means of attack actually used were very different from those originally contemplated. Diesel-operated bulldozers, big trucks, full-revolving electric shovels and electric churn drills constitute the major equipment finally purchased for this modern stripping operation. Neither the bulldozers nor the big trucks were considered in the early operating plans, for at that time bulldozers had not been used in mining operations and the trucks as yet were undesigned. The full-revolving shovel and the churn drills were not new developments in open-pit equipment, but both had undergone remarkable manufacturing transition, emerging far more efficient and far more dependable than their predecessors. Even the ordinary drilling steel had been fundamentally changed. It was now threaded so that the dulled cutting bits could be detached and replaced, thus eliminating the costly transportation of long bars to the drill shop for resharpening. The decision to use trucks in the preliminary stripping operations was based on the desirability of this type of transportation to economically prepare the pit for rail haulage, coupled with the success that the contractors had had with them on other big excavation jobs. There are at present no plans for the use of trucks beyond the preliminary work, inasmuch as rail haulage will give lower costs after roadbeds and benches are once established. For many years to come, both ore and waste haulage will be over favorable grades. The average length of ore haul between the pit and an assembly yard will be about two miles. From there the crushers will be 1? miles with a connecting track grade of 0.4 per cent. The upper ore benches of the pit will be reached from the yard by a series of four switchbacks over a ruling grade of 4.0 per cent compensated for curvature. Tracks to the dumps will be on 0.2 per cent grades.

Jan 1, 1940