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By D. T. MacRoberts

A simple disturbance in a gas reservoir travels with a finite velocity which is nearly independent of the amplitude of the disturbance. As a result very complex transients may be set up which seriously affect observation at a well. The time of transient is much longer than commonly supposed. INTRODUCTION A change in pressure at a gas well is not propagated through the reservoir instantaneously but with a definite fin- ite velocity. Knowledge of the period ! of this transient is of value because: 1. Observations of pressure and flow-rate during the transient may affect interpretation of back-pressure tests. 2. Interference effects between wells may be used to determine continuity of formation. 3. Additional information concerning the physical characteris- tics may possibly be deduced from the behavior of a well during the transient. MATHEMATICAL DEVELOPMENT It will be assumed that the well is initially closed in and that the pressure is constant throlughout the reservoir. As the initial disturbance passes outward from the well it is further assumed that a logarithmic pressure distribution is established between the most distant point reached and the well, so that: <l> = ((/)r-<t>w) I ------------ + (/) . (1) Manuscript received at office of the Branch September 15. 1948. Paper presented at Branch Fall Meeting, Dallas. Texas. Oct. 4-6, 1948. r. = distance to any point between r and rw r = radius of drainge iw= radius of well (/) = potential (P for incompressible fluids, P2 for perfect gases) Up to the time the effect reaches the point r the production from the well will be: W= (Pr-P,,,) . (2) i b W = volume produced t = sand thickness F = fractional porosity Pr = reservoir pressure Pm = average pressure between r and rw Pb = atmospheric Pressure All pressures will subsequently be stated in atmospheres and the constant Pb will be omitted. This will be produced at a rate: dw t k (Pr³-PW2) do d 0 - . (3) log — Pw = pressure at the well k = permeability 0 = time = viscosity

Jan 1, 1949

By M. J. Marcinkowski, R. M. Fisher

The flow stress-grain size relationship has been determined at room temperature in both a disordered and a fully ordered FeCo for plastic strains up to 30 pct. The results are in agreement with a Hall-Petch relation of the type given by Of =a,+kd-1/2 where of is the flour stress and a, increases mono-tonically with increasing strain to a maximum value which is much higher for the ordered than for the disordered alloy. The slope, k, is found to increase FOLLOWING the original work of Halll and petch relating the effect of grain size to the lower yield stress of iron and steel, it has been generally found that the yield stress oy.s. of polycrystalline metals with strain to a maximum and then decrease for both ordered and disordered alloys. However, k for the ordered alloy is in general higher than that for the disordered alloy and the critical strain for k max somewhat larger. All of these observations can be satisfactorily accounted for quantitatively and in some cases semiquantitatively by using a slip band-grain boundary intersection model, and by taking note of the fact that, in general, moss slip, while quite common in the disordered alloy, is extremely difficult in the ordered alloy. obeys a relation of the form oy.s.=a0+kd-1/2 [1] where a, and k are constants and d is the mean grain diameter. For convenience, and in accord with prevailing custom, Eq. [I] will be referred to simply as the Petch relation. Tjerkstra3 and Armstrong, Codd, Douthwaite, and petch4 showed that the flow stress af of iron or steel measured at strains of up to at least 20 pct also obeyed a relationship of the type given by Eq. (11. The latter investigators have also shown that Eq. [I] applies to fcc and hcp metals and alloys.

Jan 1, 1965

By C. E. Shoenfelt, E. W. Krampert

The major oil discovery in 1938 for Wyoming was the General Petroleum Corporation&apos;s So. 1 Government, C.NW.SE. of sec. 21-35N-77W, on the Cole Creek structure in central Wyoming, 14 miles northeast of Casper. This well found commercial oil production in basal Cloverly sand (Lakota) at 7978 ft. and was completed on May 28, 1938, at 8019 ft., 3 ft. in Morrison shale. It had an initial produrtion of 10 bbl. of oil an hour but at the end of a 7-day test made 336 bbl. of oil in 24 hr. During 1938, the well produced a total of 23,161 bbl. of oil. It has been agitated about 10 days out of each month to provide fuel for lease and drilling operations, the balance of the time it has been shut in pending the completion of the second well on the structure. The Cole Creek oil is of intermediate base and has an A.P.I. gravity of 32.7". The record of the well contains the "tops" listed in the accompanying tabulation. Tops in General Petroleum Corporation&apos;s No. 1 Government Well Feet 2210 Top of the Mesa Verde (Teapot sandstone) 2960 Top Steele shale 4500 Shannon sand; good show of oil and gas 6740 Top Frontier sand; some oil saturation 6840 Halliburton test of Froutier did not show much oil, but at 6878 ft. the oil showing amounted to 50 barrels 6878-7051 Shale 7051-7062 Sand with some oil saturation 7062-7920 Shale (sandy phase of Thermopolis shale 7779 to 7788 ft.) 7920-7926 Sand (Muddy); oil-saturated 7926-7974 Shale 7974-7979 Hard, coarse, limy sand (Dakota); some oil saturation 7979-7997 Soft sand; high oil saturation 7997-8002 Shale with pyrites 8002-8016 Sand (Lakota) 8016-8019 Variegated Morrison shale 5600 Elevation Lance Creek Field.—Important extensions to the Lance Creek field in eastern Wyoming were made in 1938 by the completion of a number of

Jan 1, 1939

By C. E. Shoenfelt, E. W. Krampert

The major oil discovery in 1938 for Wyoming was the General Petroleum Corporation&apos;s So. 1 Government, C.NW.SE. of sec. 21-35N-77W, on the Cole Creek structure in central Wyoming, 14 miles northeast of Casper. This well found commercial oil production in basal Cloverly sand (Lakota) at 7978 ft. and was completed on May 28, 1938, at 8019 ft., 3 ft. in Morrison shale. It had an initial produrtion of 10 bbl. of oil an hour but at the end of a 7-day test made 336 bbl. of oil in 24 hr. During 1938, the well produced a total of 23,161 bbl. of oil. It has been agitated about 10 days out of each month to provide fuel for lease and drilling operations, the balance of the time it has been shut in pending the completion of the second well on the structure. The Cole Creek oil is of intermediate base and has an A.P.I. gravity of 32.7". The record of the well contains the "tops" listed in the accompanying tabulation. Tops in General Petroleum Corporation&apos;s No. 1 Government Well Feet 2210 Top of the Mesa Verde (Teapot sandstone) 2960 Top Steele shale 4500 Shannon sand; good show of oil and gas 6740 Top Frontier sand; some oil saturation 6840 Halliburton test of Froutier did not show much oil, but at 6878 ft. the oil showing amounted to 50 barrels 6878-7051 Shale 7051-7062 Sand with some oil saturation 7062-7920 Shale (sandy phase of Thermopolis shale 7779 to 7788 ft.) 7920-7926 Sand (Muddy); oil-saturated 7926-7974 Shale 7974-7979 Hard, coarse, limy sand (Dakota); some oil saturation 7979-7997 Soft sand; high oil saturation 7997-8002 Shale with pyrites 8002-8016 Sand (Lakota) 8016-8019 Variegated Morrison shale 5600 Elevation Lance Creek Field.—Important extensions to the Lance Creek field in eastern Wyoming were made in 1938 by the completion of a number of

Jan 1, 1939

By David D. Rabb

Leaching or solution mining, a relatively simple and economical process for beneficiating metallic ores, is likely to find increasing application in the treatment of low-grade ores that are impractical to mine by any other means. This process may be carried out in two different ways: 1) dump leaching, where the ore is moved from its original location to be leached at another site; and 2) In-situ leaching, where the ore is leached in place by introducing the leach solution at the top, letting it flow down through the ore under gravity, and then recovering it plus the dissolved metals it contains. Whichever leaching method is used, it is almost always necessary to break up the ore before leaching. In this paper a study is reported which indicates that rock broken by an explosion-in particular, an underground nuclear explosion-is significantly more amenable to leaching then is rock broken by other methods. These results suggest that the leaching speed and efficiency could be increased by nuclear fracturing of the ore. Not only would the leach time be shortened, but the resulting increase in strength or richness of the solutions would decrease plant installation expense as well as reduce pumping and processing costs. A considerable fund of experience has been accumulated in the course of several hundred experimental underground nuclear explosions, so that the gross results of any given nuclear explosion can now be predicted with a fair degree of confidence.&apos; From this knowledge it seems clear that, under the proper conditions, large ore bodies can be fractured much more economically-macroscopically speaking-by nuclear explosions than by other methods. The present study concentrates on smaller scale effects that is, the cracks in the chunks of rock broken by the explosion-and shows that here too, in the microscopic domain, there are important advantages to nuclear fracturing. The intense shock produced by the very fast acting, high-brisance nuclear explosive fractures the rock in a way that should significantly improve its leachability. Experimental Procedure This study compared rocks broken by nuclear explosives with rocks produced by conventional mining, quarrying, or core drilling. The test samples, granite chunks 6 to 8 in. on a side, plus core sections, came from the area of the Hardhat*2 nuclear explosion and were taken both before and after the explosion. For comparison, several samples of quarried granite were obtained from a local gravestone monument company. The general procedure was to soak the test samples in leaching solution and then determine the extent of penetration. A standard commercial copper leaching solution was used (10 gpl Cu, 10 gpl H2SO4, 5 gpl ferric Fe, 15 gpl total Fe, pH about 1.5), to which a water-soluble penetrant dye, Zyglo 1-c, had been added. Details of the procedure were as follows: 1) Sample leached in solution containing Zyglo penetrant dye. 2) Washed with water. 3) Air-dried. 4) Cut with granite wire saw. 5) One face polished with granite monument polish. 6) Sent directly to be photographed, or heated at 110°C for 2 hr and then sent to be photographed. 7) Photographed under ultraviolet light to show crack patterns. Results After 10 days of leaching at 70-75°F, the samples were removed from the solution, washed, dried, and cut in half with a granite wire saw to study the penetration of the leach solution. Since the Zyglo dye in the leach is visible under ultraviolet light, the degree of penetration of the leach (and hence the cracks in the samples) can be studied on photographs of the crosscut samples made under ultraviolet light. The photos in [Fig. 1] show how the leach solution penetrated various representative samples. Of the 71 rock samples examined, fractures were most frequent and prominent in samples from the rubble produced by the nuclear explosion [(Fig. 1D)]. Fracturing was less apparent in shaft-mined rock [(Fig. 1B)], still less evident in drift-mined rock [(Fig. 1C)], and practically nonexistent in cored or quarried specimens [(Fig. 1A)]. The samples in [Fig. lA-C] were from the same general area as the nuclear explosion, but they were obtained before the explosion. Results of the crack studies are summarized in [Table 1]. The Zyglo-treated leach solution penetrated the test samples at the rate of about 1/2 mm during the first hour, 1 mm by the end of 4 hr, 2 to 3 mm in 12 hr, and 4 to 6 mm in 10 days, showing a progressively slower rate with time.

Jan 1, 1972

By F. R. Jones

AT Tahawus, N. Y., National Lead Co. operates the MacIntyre development. Here the world&apos;s largest titanium mine produces 5200 long tons of ore per day and pours 8000 long tons of waste rock over its dumps. Concentrated ilmenite is sent by rail to National Lead Co. pigment plants, and a second product, magnetite, is sold to steel producers in raw form or is agglomerated and shipped as sinter. Several earlier attempts had been made to produce iron from the deposits, which have been known since 1826. These attempts failed, chiefly because of titanium impurity. In 1941 the present owners reestablished the operation for production of war-scarce ilmenite, and the impurity became the main product. The Ore: The MacIntyre ore zone is about 2400 ft long and 800 ft wide in horizontal measurements. Ore outcrops were found on the northwest side of Sanford Hill, 450 ft above Sanford Lake and 2500 ft southeast. The zone dips at about 45" toward the lake and plunges to the southwest. The ore minerals, ilmenite and magnetite, are unevenly distributed in bands roughly parallel to the long axis of the ore zone and are interspersed with bands and horses of waste. Hanging wall ores are fine grained and grade from rich ore to waste rock or gabbro. Footwall ores are coarse grained and are almost entirely ilmenite and magnetite. The foot-wall waste rock, anorthosite, is the common country rock. Several faults cut the ore zone. These faults have no great displacement but do contribute to the great physical variations in ore rock and surrounding waste. The Mine: The MacIntyre mine is an open pit operation, with benches at 35-ft intervals. The lowest bench is now 54 ft below lake level. Loading equipment consists of three electric-powered shovels (a P & H model 1400 with 4-yd dipper and two Bucyrus-Erie models 85-B with 2%-yd dippers) and one diesel-powered shovel (a Northwest model 80D with 2%-yd dipper). Ore and waste are transported to a 48x60-in. jaw crusher in ten 22-ton Euclid trucks with 300-hp diesel engines. Ordinarily the two Bucyrus-Erie 2 % -yd shovels load ore into a fleet of three or four trucks. This combination works two 8-hr shifts per day, moving 5200 long tons of ore to the crusher and removing a small portion of the waste rock. The P & H model 1400 shovel, with a fleet of four trucks, loads waste on three shifts per day. The mine operates on a 5-day week, with a small maintenance crew working Saturday. Oversize rock is broken by a dropball handled by an Osgood model 825 rubber-mounted crane.&apos; Ore and waste are broken by drilling and blasting 9-in. diam vertical holes behind the benches. Bucyrus-Erie 42-T churn drills are used to drill the holes, which are extended 4 ft below the bench level on which the broken rock will fall. Drilling and Blasting History: In its early years the mine was equipped with Bucyrus-Erie 29-T churn drills, which drilled 6-in. holes. To keep up with production requirements the hole diameter was soon increased to 9 in., and by 1950 the three 42-T drills now in use had been acquired. Early blasting experiments with different kinds and grades of explosive led to adoption of 90 pct straight gelatin dynamite as standard. It was recognized that this explosive was expensive, and from the start of operations until 1950 extensive experiments were made using blasting agents of the ammonium nitrate family. Results were recorded as uniformly poor, with great build-up of oversize rock. The expense of these experiments, and the discouraging results, caused the abandonment of any expectation of breaking MacIntyre rock with anything but 90 pct straight gelatin dynamite. Further standardization led to 9-in. well drillhole spacings set at 16 ft in ore and 18 ft in waste, exceptions being permitted only for unusual conditions. The hole burdens were theoretically about 22 ft. Due to the extreme back-slope of bench faces, caused by blasting with heavy charges of dynamite, actual burdens were commonly well over 30 ft. Lack of precise control resulted in many holes having a burden as light as 15 ft. General practice was to stem 6 or 7 ft of hole with magnetite concentrate, the amount of stemming being left to the discretion of the pit foreman. Usually all holes in a row were fired instantaneously with Primacord detonating fuse. Millisecond delays were

Jan 1, 1957

E O&apos;C Acker &apos;86 Jinzoc Adachl &apos;88 Frederic R Abbe &apos;97 T H Aldrich &apos;96 Truman H Aldrich &apos;78 Walter H Aldridge &apos;89 Anson W Allen &apos;87 John H Allen &apos;84 Thomas Andrews &apos;94 William R Appleby &apos;90 R M Atwater, Jr &apos;97 Lawrence Austin &apos;82 S Ayres &apos;73 H Foster Bain &apos;97 David Baker &apos;86 John Henry Banks &apos;83 Henry C Banon &apos;90 Thomas J Barbour &apos;97 Alonzo F Bardwell &apos;89

Jan 1, 1952

By R. C. Ernrnons, Ray Wilcox

RECENTLY completed experimental work, carried out in the department of geology at the University of Wisconsin, aiming at a prevention of silicosis in industry has been reported in the American Mineralogist. A vast amount of work on silicosis has been reported in the literature, the clinical aspects having been especially well covered. A host of critical observations have been made on the variations in the nature of the silicosis problem in different environments, and a great deal of valuable experimental work has helped to clarify these observations. At present a greater amount of information of a critical sort is available than ever before, which affords a more sound basis for interpretive thought. It has been observed in industry that essentially pure silica dust gives rise to silicosis. Jones would modify this conclusion to place the responsibility on sericite, a silicate mineral present in the siliceous dust. Material such as granite dust, which carries a high free silica (quartz) content, is also a silicosis hazard. But sericite, too, is usually present in granite. In general it is widely believed that silicosis is caused by the presence in the lung of silicic acid regardless of the source. This view is adopted here.

Jan 1, 1937

By P. J. Potter

Practically all tin-base babbitt metals used in engine bearings are made to customers&apos; specifications, which are many and varied. The copper ranges from 3 to 8 per cent. and the antimony from 4 to 13 per cent.; generally, the babbitt with lower copper content will contain from 4 to 8 per cent. antimony and that with higher copper will have from 7 to 13 per cent. antimony. The allowable lead content varies from 0.20 to 2.00 per cent. If a solder is used as a bonding material instead of tin, the resulting material in the finished bearing will have a higher lead content, but it would not be enough to bring the lead above specifica-tional limits. Impurities such as iron, arsenic and bismuth should be determined in the tin before using to insure a uniform and high-grade product. These points must be considered when segregating and grading the waste that comes from the finishing operations on lined bearings. Classification of SCRAP Because of the extremely rigid nature of most of the specifications for bearing linings it is necessary to use the purest of materials as a base for all compositions. The problem of handling secondary metals is confined almost entirely to the recovery of drosses, spills and turnings incident to the manufacturing operations. As a matter of convenience the waste or scrap may be divided into 10 grades, as follows: 1. Tin from pots where tinning operation is carried out. 2. Tin and babbitt spatters from babbitting operation. - 3. Tin skimmings combined with burned zinc chloride. 4. Borings and reamings. 5. Gates from die-cast bushings and bearings. 6. Drosses from die-cast pots, babbitt foundry pots, and pots in babbittiug room. 7. Babbitt with small amount of bronze from machining operations. 8. Babbitt and bronze borings. 9. Scrap bronze-back babbitt-lined bearings. I 10. Scrap die-cast bearings and bushings. A few of these grades of salvaged material have compositions that make it possible to determine beforehand where they may be used to

Jan 1, 1930

By W. C. Meyer

In an effort to conserve and extend oil resources, the use of powdered coal-in-oil mixtures (COM) as an alternate fuel in oil-fired boilers is receiving increasing attention. For the approach to be successful, some degree of stability of the suspension against settling is needed. The variety of means available to achieve stability of this nonaqueous slurry is reviewed along with some of the physical and chemical concepts which underlie each method.

Jan 1, 1983

Discussion of the paper of Robert R. Abbott, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2389 to 2400. ALBERT SAUVEUR, Cambridge, Mass.:-Mr. Abbott has certainly made a strenuous effort to ascertain the influence of the various elements on the absorption of carbon by steel-a subject of great importance to those dealing with the case hardening of that metal. Because of the extensive and careful character of Mr. Abbott&apos;s experiments, one is all the more disappointed that his results, as he himself recognizes, are not more satisfactory; for, indeed they leave us just about where we were,-still entertaining uncertain views in regard to the carbon-absorbing power of various alloy steels. It might be asked whether Mr. Abbott&apos;s method of estimating the amount of carbon absorbed-namely, by weighing the specimens before and after the carburizing treatment-was the best one to select. Are not serious sources of error. inherent to such procedure because of the difficulty of satisfactorily removing the earburizing material attached to the specimen ? The method of least squares has certainly failed to solve the problem satisfactorily. By manipulating Mr. Abbott&apos;s results in a different manner I have obtained the following expression: P = 100 - 50 C - 7 Ni + 20 Cr, in which P represents the carbon-absorbing power; C, the percentage of carbon; Ni, that of nickel; and Cr, that of chromium. It is assumed that the carbon-absorbing power of pure iron, or what might be called its carburizability, is represented by 100. Applying the formula, for instance, to a steel containing 0.15 per cent. C, 3 per cent. nickel, and 0.50 per cent. chromium, its carbon-absorbing power would be 100-50X0.15-7X3+20X0.50=81.50; that is, 81.50 per cent. of the carbon-absorbing power of pure iron.

Jan 12, 1913

ALABAMA Alabama City.-Eddy, L. Altoona.-Cain, J. America.-Foreman, J. T. Anniston.-Foster, R. N. Ashland.-Sturdevant, J. C. Bessemer.-Ball, E. M. Calhoun, F. W. Maschmeyer, W. L. McKenzie, W. C., Jr. Birmingham.-Abbott, C. E. Aldrich, T. H. Aldrich, T. H., Jr. Ashton, J. J. Aufderhaar, H. C. Ball, T. L. Biddison, P. M. Blair, C. S. Brown, T. S. Bush, M. W. Clark, G. H. Crawford, G. G. Crockard. F. H.

Jan 1, 1929

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,&apos; Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.&apos; In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,&apos; employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,&apos; i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,&apos;&apos; was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

E. H. Dix, JR., Chairman L. W. M. PEIRCE, Past-chairman R. F. MEHL, Vice-chairman ALBERT J. PHILLIPS, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer LOUIS JORDAN, Executive Secretary 29 West 39th St., New York, N. Y. Executive Committee W. H. BASSETT, JR. R. H. LEACH&apos; W. H. FINKELDEY W. E. REMMERS2 J. A. GANN H. J. ROAST G. O. HIERS C. S. SMITHS L ZICKRICK

Jan 1, 1936

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration&apos; was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1&apos;2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult&apos;s law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.&apos;- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin&apos; has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled&apos; that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By A. H. Bromly

THE small agricultural village of Santa Barbara, in the State of Guanajuato, has been the center of spasmodic tin-mining operations during recent years. The deposits, so far as I know, are unique, and a few brief notes may be of interest. Santa Barbara, about 12 miles west of San Felipe station on the Mexican National Railway, and at an elevation of 2,400 m. above sea-level, is situated in a flat valley extending east and west, and bounded north and south by broken rugged bills rising about 330 m. above the general level of the valley. Tin-mining operations have been conducted-at the Queensland mine, near this village. A small concentrating-mill was erected and attempts were made to smelt the ore in reverberatory furnaces. The country-rock of the district for many miles is rhyolite of great thickness. There are some local variations due to differences in cooling, or subsequent alteration or impregnation; but throughout the whole district the principal constituents of the rocks remain the same, viz., free silica, orthoclase-feldspar and sanidine. The latter is especially marled. The crevice and joints of the rock are frequently filled with calcedonic and opalescent quartz. The ore-formation at the Queensland mine is of an unusual nature, consisting of cracks in the rhyolite which have been filled with clay. This phenomenon is largely developed over a width of from 80 to 100 m., in which the principal fissuring follows an approximate direction of north and south. The av¬erage clip ranges between 70 to 80 degrees. Some of the fissures bold sufficiently true for a time to afford the impression that they are clue to dynamic causes, or earth-movement. This may be true of some of the north by south fissures; but considering

Jul 1, 1905

By R. E. Gilchrist, R. R. Harvey, M. R. Dean

A simple and rapid three-component analysis procedure has been developed for use in fluid-flow studies. The method is based on refractive index measurements, combined with refractive dispersion measured between the Ha and H wave lengths. The procedure requires. calibration curves for the three-fluid system. The only restriction on the fluids employed is that only one be an aromatzc or olefinic compound. Individual sample measurements require only a few minutes. Composition results within the limits of accuracy required for fluid-flow analog studies are obtained. INTRODUCTION The simultaneous analysis of three-component mixtures is a problem often encountered in fluid-flow analog systems. In petroleum production research, the problem is usually encountered in experiments on the displacement of fluid from a porous medium. In the case of immiscible displacement, simple volumetric measurements of the produced fluids are usually sufficient, the analog fluids often being the actual reservoir fluids themselves — oil, water and gas. However, modern secondary recovery of petroleum sometimes involves production under miscible conditions, in which the oil is displaced by liquefied petroleum gas which, in turn, is displaced by dry gas. Since this type of displacement is done under conditions of pressure and temperature that are not easily reproduced in the laboratory, studies are often performed with analog fluids at essentially atmospheric pressure. Since the number of samples taken during one of these experiments is usually quite large, the time required for analysis becomes an important factor. In the past, the difficulty of conventional analysis has been avoided by the addition of various tracers to one or more of the components, or by the use of a tracer fluid as one of the components. With these techniques, a relatively large amount of analytical time is still required. Moreover, in the case of added tracers, the tracer material may migrate in part to one of the other fluids, may be adsorbed on the solid surfaces of the model, or may introduce side effects not characteristic of the prototype fluid. The substitution of a tracer fluid for one of the components can severely limit the choice of analog fluids. Optical refractometry provides a rapid and economical method of analysis of two-fluid systems or of monitoring small changes in composition of an essentially one-component system. Refractometric methods are capable of high degrees of accuracy, require only very small samples and can easily be adapted to automatic methods. They are not generally applicable, however, where three or more fluids are present over wide ranges of concentration. The method of three-component analysis described here has three essential characteristics. 1. It is based on refractometric measurements and thus preserves all of these desirable properties. 2. It does not make any stringent demands on the choice of fluids that can be analyzed. 3. It is capable of accuracy sufficient for fluid-flow analog studies. THEORETICAL The difference in the refractive index of a substance at two different wave lengths of light is known as its dispersivity. When the difference is taken between the specific refractions at the two wave lengths, the quantity is referred to as the specific dispersivity. Specific refraction was defined empirically by Gladstone and Dale1 as r = n-1/d....[1] where n is the index of refraction and d is the density. The definition is given more correctly by the expression r =n2-1/n2+1 1/d..........(2) 1References given at end of paper. MICIFTV OF PETROLEUM ENGINEER JOURNAL.