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By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By P. F. MINISTER

AT Lime Spur, Mont., the East Butte Copper Mining Co. has been quarrying limestone for twenty years. The quarry is beside the Northern Pacific R. R. in the Jefferson River canyon, 4 ½ miles east of Cardwell, at Lime Spur, Montana. HISTORY This quarry was opened early in 1900 by Dan Morrison of Whitehall, the discoverer of the Morrison cave, to supply a demand for smelter flux. Limestone was sold to the Pittsmont smelter of The East Butte Copper Mining Co. and to the Butte Reduction Works. As no particular effort was made at the quarry to select the rock that delivered to the smelters was unduly high in magnesia and impurities. The East Butte com¬pany, therefore. Bought the quarry. in 1909 and confined operations to the high-grade beds in order to supply rock of the desired purity for its own smelter and the Butte Reduction Works until the latter shut down. It also developed a market for some of its rock with the sugar factories. The latter market increased until in later years all rock, larger than 4 in. in size over a bar grizzly, was being shipped to the sugar factories, and the rock smaller than 4 in. was being used as a flux in the blast furnaces at the Pittsmont smelter. In 1924, the East Butte concluded a contract with the Anaconda company for the treatment of its ores, and the Pittsmont -smelter -was shut down: which made the minus 4-in. rock a useless by-product. Since there was not enough revenue in the sugar rock alone and also because of limited waste room it became necessary, if Lime Spur was to continue to operate, to increase- the proportion of plus 4-in. rock and to develop a market for the minus 4-in.

Jan 1, 1930

By AIME AIME

The XCVIIth meeting of the Institute for the reading and discussion of papers will be held at Spokane, Wash., beginning Monday, Sept. 27, 1909, as already announced in Special Circulars of May 8 and Aug. 14, 1909, and in the Bulletins for June, July, and August. The meeting will be preceded by a tour through Yellow stone Park and visits to Butte and Anaconda, and will be followed by visits to the Coeur d'Alene district, to the Alaska-Yukon-Pacific Exposition at Seattle, to the mining- and smelting-plants near Salt Lake, and to the iron- and lead- and zinc-plants at Pueblo. The special train for the party' will leave Chicago, September 16, and return about October 12. Details of the itinerary are given later in this announcement. The Secretary of the Spokane Local Committee is Lyndon K. Armstrong, 615 Hyde Block, Spokane, Wash., to whom should be addressed all inquiries concerning local matters. The control of the papers and proceedings will remain in charge of the Institute office, as usual. It is greatly to be desired, both in behalf of the Institute and in recognition of the many courtesies to be extended on the trip, that the excursion party be made larger. Exceptional facilities to visit the many mines and smelters have been freely provided; and members are requested to make all reasonable effort to attend the meeting at Spokane and participate in the excursions. For those who cannot join in the entire trip, it may be possible to provide special Pullman accommodations after leaving Yellowstone Park. In order to make the necessary arrangement, however, the names of members and guests contemplating this partial trip should be sent at once to Theodore Dwight, 29 West 39th Street, New York City. The general cost of the trip per member will be $300, which includes transportation, berth, and meals for the entire trip from

Sep 1, 1909

By A. Lubinski, C. R. Stewart, K. A. Blenkarn

Storage porosity has been considered one of the important pore geometry characteristics of heterogeneous-porosity limestones. Storage pores are only containers for fluids, in contrast to flow channel pores which both contain fluids and provide continuity for fluid flow. The concept of another geometry characteristic, "poro-striction", is presented as a second pertinent variable in describing limestone pore space. In simple terms, poro-striction is a measure of the flow resistance between storage and flow channel pores. Alternating-flow core-testing theory provides flow relationships which can be used to divide the pore space of heterogeneous-porosity media into flow channel and storage pores and to measure the "porostriction" of the latter. Experimental application of this theory to naturally occurring heterogeneous limestones shows that "porostriction" and the ratio of storage to flow channel pores can be estimated. Porostriction and porosity ratio are microscopic characteristics which should influence oil-recovery efficiencies during certain types of displacement processes. A knowledge of pore geometry should be valuable in designing or selecting the most effective oil-recovery process for heterogeneous limestones containing storage porosity. INTRODUCTION The primary and secondary recovery of oil from limestone (carbonate) reservoirs has been and will continue to be a major source of the world's supply of petroleum. Oil recovery from this type of formation is strongly influenced by the size, shape and arrangement of the pore spaces which hold the formation fluids. Therefore, it is expected that better knowledge of pore geometry would lead to design of more effective recovery processes. The concept of storage and flow channel pores has been presented as an important characteristic of limestone porosity.1 In this concept, storage pores are only containers for fluids, whereas flow channel pores are those pores which both contain and transmit the fluids. The work reported herein involves the concept of an additional pore characteristic called "porostriction". This characteristic can be visualized as the flow resistance between the storage and flow channel pores. This resistance is an important pore geometry characteristic because it determines how easily gas and oil can replenish fluids removed from the flow channel pores. Fatt and co-workers at the U. of California have studied the effect of storage porosity and a factor similar to porostriction on transient-flow response of models of porous media during a pressure build-up or drawdown test.55 These models consisted of porous sandstone cores with artificially simulated storage pores. It is the purpose of this paper to describe tests which permit the storage porosity and porostriction of actual reservoir core samples to be estimated. The tests used for this purpose involved not transient tests but, rather, an alternating-flow technique in which pressure and flow are varied according to a sine-wave relationship. This technique may offer advantages over transient methods. THE POROSTRICTION CONCEPT Before discussing alternating-flow (A.F.) tests in core samples, it is necessary to define the porostriction parameter. For this purpose attention is focused upon an elemental volume v representative of a porous medium having both flow channel pores and restricted-access storage pores. For such an elemental volume, it is considered that the storage porosity is combined to form a single pore and that the access into the storage porosity may be represented by a single capillary tube connecting the single pore to the flow channels of the elemental volume. Let the radius of the capillary tube be designated as Rc and its length as L,. When fluid flows into or out of the pore, the following equation (Poiseuille's law) relates flow rate q to pressure drop p, and the physical characteristics of the tube and the fluid of viscosity jx.

By A. H. Bell

Continued low prices and restricted markets for crude oil discouraged drilling activity in Illinois oil fields during 1933. Only 36 wells were completed in the state, the smallest number since 1904, and of these the majority were scattered wildcat wells, only 10 having been drilled in producing fields (Table 2). Production was curtailed approximately 40 per cent for the first half of the year. During July, August, and the early part of September there was no restriction on production. On Sept. 8, under the "code of fair competition for the petroleum industry," the quota of allowable production for Illinois was fixed at 12,000 bbl. per day. The state's production in 1933 was 9 per cent less than in 1932. What it would have been had there been no curtailment of production and if economic conditions had permitted a normal amount of cleaning out and repairs to wells, it is not possible to estimate, but it would no doubt have been considerably more than the actual figure. No new pools or new producing horizons were discovered in 1933, but the deepening of a Robinson sand well in Crawford County to the McClosky "sand" horizon (St. Genevieve limestone of the Lower Mississippian) resulted in a production of 3 bbl. per day (Fred Patchel, Savilla Shipman No. 5, NE. 1/4, SW. 1/4, sec. 26, T.6N., R.l3W., deepened from 1122 to 1388 ft., to be tested to the McClosky horizon, and, owing to the rapid variations in porosity within short distances, as shown in the Lawrence County field to the south, one test may not be considered as proving or condemning any large area. The average price of Illinois crude oil in 1933, calculated from the posted prices as published in the Oil and Gas Journal and Oil Weekly, was $0.862 per barrel. This compares with a calculated average price of $1.032 in 1932 and 0.852 in 1931. The total value of Illinois crude oil produced in 1933 obtained by multiplying the average price (0.862) by the total production (4,227,000 bbl.) was $3,643,674. Of the 26 wildcat wells drilled in 1933, only one was drilled on known favorable structure. This was the Walmar Oil Company's William Pepple well No. 1, sec. 12, T.4N., R.12W., Hancock County, which tested

Jan 1, 1934

By J. C. McKinnell

The appraisal of an oil lease may often be mad,? through production decline analysis, which requires description of the functional relationship between the oil production rate and either cumulative production or time. Heretofore, attempts to define the function appropriate to a given set of production data have depended to some extent on subjective procedures. The purpose here is to introduce an objective solution, obtained by combining the principle of least squares with the theory of equations. MATHEMATICAL ANALYSIS The fundamental differential equation appropriate to a general class of decline curves may be written. Solution of Eq. 1 for general boundary conditions may be written in terms of either the cumulative oil production or time: These equations constitute the mathematical expression of the so-called hyperbolic decline. Their complete description for a given set of production data requires the numerical evaluation of the three parameters1.', n, D, and (go),. For the special case of n = 0, Eq. 2 becomes q. = (q.), - DiN with the corresponding expression in terms of time being q. = (qa),e...........(5) Similarly, for the special case of n = 1, Eq. 3 becomes with the corresponding expression in terms of cumula- tive oil production being q. = (q.),e " '.......(7) Eqs. 4 and 5 constitute the mathematical description of the so-called exponential decline; Eqs. 6 and 7 are the mathematical description of the harmonic decline.',' Returning to the hyperbolic expressions, Eqs. 2 and 3 may also be written, q: = sNp + b........ (8) and where a = 1 - n; s = (n— 1)D,(q0);"; b = (go):-"; a'=-n;s/= nD,(qo);"; and b' = (go);-. Note that both Eqs. 8 and 9 are linear in either time or cumulative production with respect to an exponential function of the production rate. In other words, a straight line relationship results for both variables when associated with the appropriate power of q,. This fact is of prime importance in the application of statistical analysis. . STATISTICAL ANALYSIS For a given oil lease, the time, production rate and cumulative production are recorded records. To establish predictive formulas from Eqs. 2 and 3, it remains to determine numerical values for the three parameters [n, D, and (q,) .] through an investigation of the past history. Upon interpreting a, s and b as parameters, Eq. 8 may be expressed for every time interval of interest, i, over the past history as follows. (q,): = s(Np), + b........(10) In general, Eq. 10 will not be satisfied exactly, because of the assumptions in the expression of Eq. 1, and the errors and anomalies universally associated with production data. It will instead define the residual, s(Np), + b- CO=d......(11) Squaring both sides and summing over all the data points, m, under consideration yields

By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.', ' No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers' it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.' The majority of values reported in the literature7-', ' were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.' cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

By C. S. Smith

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

Jan 1, 1960

By N. S. Stoloff, R. G. Davies

A study has been made of the efject oj different dislocation-precipitate interactions upon the temperature dependence of the flow stress of aged Ni-14 at. pct A1 alloy. It is observed that when the dislocations bow between widely spaced (-20004 coherent Ni3Al particles the flow stress decreases with increasing temperature in the normal way. However, when the dislocations cut closely spaced (-5004 particles the flow stress is independent of temperature from -100 to 600°C, due to a balance between softening of the matrix and an increase in strength of the particles with increasing temperature. The retention of strength at high tempera-tures of commercial nickel-base alloys, which are strengthened by the precipitation of a phase based upon Ni3Al, is thought to be due to the unusual strength properties of Ni3Al. The flow stress of Ni3Al increases continuous1y from -196"C to a maximum at -600"C. It is concluded from a series of thermal-mechanical tests that the sevenfold increase in flow stress over this temperature interval is due to a lattice effect and is not diffusion-controlled. The flow stress of precipitation- or dispersion-hardened materials depends on the resistance to dislocation motion within the matrix and the extra energy required for dislocations to bow between or to cut particles. If the dislocations bow between the particles or if the strength of the cut particles is constant with temperature, then the flow stress of the precipitation-hardened alloy must decrease with increasing temperature due at least to the decrease in elastic modulus of the material. There will be softening also from thermally activated cross-slip or climb, offering an additional degree of freedom for dislocations to avoid particles. For example, in the case of nickel containing a dispersion of thoria,' which most probably deforms by dislocations bowing between particles, the flow stress decreases by about 50 pct between 25" and 650°C. In A1-Cu alloys2 aged to produce the 8" precipitate, dislocations cut the particles, and the flow stress decreases by about 20 pct between -269" and 25°C. However, many commercial high-temperature nickel-base alloys, for example Inconel-X and Udimet-700, exhibit little or no decrease in flow stress with increasing temperature up to about 700°C. A characteristic feature of these alloys is that they are strengthened by the precipitation of a phase based upon Ni3A1. Guard and westbrook4 and flinn' have shown that Ni3Al (and alloys in which a third element such as molybdenum or iron is substituted for part of the aluminum) is unusual in that the hardness and flow stress increase with temperature to a maximum at about 600°C. For the flow stress of a precipitation-hardened alloy to be independent of temperature we propose that the particles must be cut by dislocations moving through the matrix and that the strength of the particle must increase with increasing temperature. Theories of precipitation hardening do not take into account the flow stress of the dispersed particles that are cut during deformation; the only dissipative process usually considered7 is the creation of interface within the particle and between the precipitate and matrix. The purpose of the present investigation has been to study in detail the temperature dependence of the flow stress of a nickel-base alloy strengthened by the precipitation of Ni3Al in two structural conditions such that when deformation occurs it does so by dislocations a) bowing between the particles and b) cutting the particles, respectively. A simple binary Ni-14 at. pct A1 alloy was chosen because considerable information is already available for this system concerning phase equilibria and precipitation reactions and rates.' Dislocation-precipitate interactions in the binary alloy should be similar to those in the more complex commercial alloys. In addition, the mechanical and physical properties of NisAl were studied in detail in the hope of elucidating the mechanism by which the strength increases with increasing temperature up to 600°C. EXPERIMENTAL PROCEDURE For the study of the effect of precipitation of Ni3A1 upon the temperature dependence of the flow stress, an alloy containing 14 at. pct A1 was utilized; a Ni-8 at. pct A1 solid-solution alloy was employed as a comparison material. Vacuum-cast ingots were hot-rolled at 1000°C and cylindrical compression samples, 0.20 in. diam by 0.40 in. high, were prepared from the 1/4-in.-diam rod. Specimens were recrystallized and solution-treated at 1000°C for 1/2 hr and then water-quenched. A preliminary study revealed that, when the Ni-14 at. pct A1 alloy was aged for 1 hr at 700°C, significant precipitation hardening was obtained, and that the structure was free from grain boundary discontinuous precipitation; an overaged condition was produced by annealing the aged specimens at 850°C for 1 hr. To circumvent the difficulties involved in the hot rolling and swaging of Ni3A1, compression samples,

Jan 1, 1965

By Simon D. Strauss

What are future prospects for U.S. mining? In many quarters the assumption is made that this country has passed its zenith as a mineral producer -- that it is in a period of decline and that it is becoming a have-not nation like Japan and much of Western Europe. These industrial rivals of ours must depend almost entirely on others for their mineral supplies. In trying to answer this question one must of course distinguish between resources and productive capacity. In today's volatile and competitive markets, the definition of what are reserves and what are merely identified resources becomes ever more difficult. Many large deposits have been found that are unlikely to be viable in the marketplace under normal conditions but that can be of significance to the nation's military and industrial security in times of emergency. I should like to draw on personal experience from World War I1 for illustration. 4fter Pearl Harbor great concern developed over the availability of a long 1ist of strategic materials for which this country was largely dependent on imports. Included were a number of minerals of which domestic deposits had been identified. Among these were chromite, manganese ore, mercury, mica and tungsten.

Jan 1, 1982

By Kenneth S. Ritchie

The natural emulsion samples used in this study were shipped directly from twelve California oil fields, through the courtesy of the superintendents of the main producing companies in those fields. Representative parts of each sample were chosen for the slides. Preparation of the slides was generally made in less than two minutes, including time of exposure; in a few cases, about five minutes was required. The short time was intended to minirmize the changes in conditions. Whenever comparison was of value, standard conditions were established. Spreading by gravity was adopted instead of smearing. Cover glasses were not allowed to rest on the films. General Characteristics of Emulsions The main purpose of the general views (Figs. 1-16) is to illustrate the general characteristics of the dispersed droplets together with any other constituent or impurity that may be found in each emulsion. The magnification is given so that dimensions could be measured from the plates. The slides used for these views had spherical recesses; they gave the best light. Where crystals were intended to be shown in the picture a filter (green was the best') was usually used. Emulsions that showed a tendency to move by concentrated light were pictured without a condenser.

Jan 1, 1931

By Wilson Blake

A mathematical model based on the finite element method of stress analysis has been used to describe the behavior of the western wall of the Kimbley Pit as its slope was steepened from 45° to 57°. Theoretical stress changes because of slope modification are slight except at the toe of the modified slope. Magnitudes of stress created are small when compared with the strength of a competent rock. Resulting displacement patterns point out the need for determining the in-situ state of stress at a site prior to excavation or modification. A comparison of model results with field measurements shows that, in general, the model has described the measured behavior of the west wall of the Kimbley Pit remarkably well. The Bureau of Mines and the Kennecott Copper Corp. began joint research on open-pit slope stability at the Kimbley Pit, Ely, Nev., in 1961. The initial or planning phase of this research dealt with a detailed geologic study of the Kimbley Pit, determination of in-situ stresses in the district, laboratory and field tests to determine rock properties, and the design of a full-scale experiment to study the behavior of this pit as its western wall was steepened from 45° to 57°. Fig. 1 shows a cross-section of the original pit outline, the steepened pit outline, major geologic features, and the two instrumentation adits. After the final or slope modification phase of the research began, a laboratory research program was initiated to develop a mathematical model that would analytically describe the behavior of the pit as its western slope was steepened. This theoretical model study of the slope modification at the Kimbley Pit was conducted with the finite element method of stress analysis. The results are described in this report.

Jan 1, 1969

By F. W. Jessen, C. A. Johnson

The effect of treatment with ferrochrome lignosul-fonate on both sodium and calcium bentonites has been examined. In the early stages of treatment it appears that some base exchange of iron and chromium for sodium may occur with the sodium bentonite. Such exchange appears specific for exchange of sodium ions when the calcium ion concentration represents 40-5.5 per cent of the total exchangeable cations, and when additions of lignosulfonate are less than 1 lb per bbl. Adsorption appears entirely physical above 1 lb per bbl treatment level for all concentrations of calcium studied. Gel strength and plastic viscosity of both calcium and sodium bentonite systems were reduced with treatments of ferrochrome lignosulfonate up to 2 Ib per bbl, the greatest reduction occurring within a range of calcium concentration of 40-5.5 per cent of the total exchange capacity of the clay. INTRODUCTION The problem of control of viscosity and gel strength of drilling fluids by the action of thinners or dispersants has been studied by many investigators.1-7 In addition, much work has been done on formation of gel structure in clay suspensions. However, gel formation and structure still are incompletely understood, and the use of the various dispersing chemicals is based, to a large extent, on data almost entirely empirical in nature. In recent years the lignosulfonates have become increasingly important in the treatment and control of drilling fluids. More specifically, ferrochrome lignosulfonate has found rather wide acceptance, particularly in calcium systems.5-7 Lignosulfonates are refined lignin products made from spent sulfite liquor from which the fermentable sugars have been removed.15 The exact structure of lignin is not known; however, it is believed to be a phenolic propane type polymer which may exist as a branched chain or cross linked structure. The molecular weights of lignosulfonates probably range from 300 to 100,000 or more.15 A better understanding of the mechanism of adsorption of dispersants is essential before improvement and development of characteristics of drilling fluids and drilling fluid control is possible. This investigation was undertaken to determine the action of ferrochrome lignosulfonate on sodium and calcium montmOrillonite' LABORATORY INVESTIGATION A Stormer viscosimeter and Fann V-G meter were used to measure viscosity and gel strength. A Zeiss spectrophotometer was used for analysis of Fe and Cr and the flame attachment was employed in the analysis of Na, Ca and Mg. A General Electric X-ray diffraction unit utilizing Copper Ka radiation and a Ni-filter was utilized in the X-ray studies. PROCEDURE Two systems were studied. Predominately sodium clay, obtained from Wyoming, and a predominately calcium clay from Texas were used. These particular samples were chosen because of the extensive work of characterization completed by Mungan. Ionic base exchange capacity determined by flame photometry and total exchange capacity by the Kjehldahl method were obtained experimentally. A 7-per cent suspension of the sodium clay and a 20-per cent suspension of the calcium clay in distilled water were prepared by mixing with a high-speed mixer. The suspensions were allowed to stand for two weeks for complete hydration. Calcium chloride was added to portions of the sodium and calcium cla suspensions to obtain suspensions varying in Ca++ concentration as shown in Table I. A series of treatments was run with 500-ml portions of the original suspensions using a ferrochrome lignosulfonate. Treatment was carried out in the same way with each of the suspensions of varying Ca concentration. Viscosity and gel strength were measured and a filtrate obtained at each treatment level. Ten ml of filtrate were diluted to 50 ml, and aliquot portions of the 50 ml were taken for the Na, Ca, and Mg analysis by the flame photometer. The pH of these filtrates ranged from 7 to 7.3. Standard

By J. E. Lamar

THAT Illinois is an important mineral producing state is well known. A value of over $237,000,000 for the mineral products in 1926 indicates the magnitude of the industries. Coal mining is the largest mineral industry, and the value of its product was about 63 per cent of the total mineral production of the state. Oil and gas constituted about 8 per cent and the non-metallic minerals about 29 per cent. This 29 per cent represents the production of a varied group of mineral industries of wide geographic distribution through the state.

Jan 1, 1929

Coal - Surface Mining Coal Preparation Coal Utilization Research and Development Health and Safety

Jan 3, 1976

By Auguste J. Rosh

The use of titaniferous ores in the blast-furnace has been the subject of much controversy for many years. Divers objections have been raised against them, and, for one cause or another, the verdict

Jan 1, 1893

By H. A. Pearse

NORMALLY, the Britannia ore mixture contains chalcopyrite and pyrite as the chief sulfide minerals, together with minor amounts of gold and silver and a low zinc content. Reduction is accomplished by jaw crushers underground, followed at the concentrating plant by Symons cone crushers, rolls, and ball mills. The standard flotation practice, evolved during several years of experimentation, provided for bulk flotation of the two sulfides, after primary grinding to only approximately 35 mesh, followed by regrinding of the bulk concentrate, with subsequent separation of the chalcopyrite and pyrite to make a marketable concentrate of each mineral. This so-called standard milling practice has previously been described in detail in U. S. Bureau of Mines Information Circular 6619. A modification will he discussed here. In the face of a constantly increasing world surplus of copper and a steadily falling price during 1930 and 1931, it was obviously undesirable to continue unprofitable production of large quantities of this metal. On the other hand, company officials were

Jan 1, 1934

By M. R. Geer

Coal washing assumed an important role in the mining industry of the Pacific Northwest long before washing practice became firmly established in the Appalachian field. A Scaife washer was operated in the state of Washington in 1887; and by 1927, the fist year for which complete statistics were compiled, nearly a third of the state's coal production was washed, in comparison with only about 5 pct for the country as a whole. Mechanical preparation was adopted in Alaska in 1922 in a plant constructed by the United States Navy at Chickaloon to provide bunker coal for naval forces operating in northern waters. Many of the coal beds mined in Washington and Alaska contained more impurities than those mined elsewhere, and this circumstance contributed to the early interest in mechanical cleaning. A much more important factor, however, was the inclination of the coal beds. With steeply pitching beds, hand sorting by the miner at the face is impossible; consequently, all material must be loaded and dealt with on the surface, just as is now proving the case with mechanical mining of flat beds. Thus "full-seam" mining afforded the same stimulus to the early development of coal washing in the Northwest that - it is providing under mechanization in the rest of the country today.

Jan 1, 1949