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By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

Apart from the general cooperation received in many quarters, the Unitization Committee desires to make specific acknowledgment to the following individuals for assistance rendered in the study to this time. California.—Committee members: Joseph Jensen, chairman, L. L. Brundred, E. M. Butterworth, H. Norton Johnson, D. B. Myers, W. R. Wardner; others who contributed: C. R. McCollom, F. C. Merritt, E. B. Noble, Ralph Arnold, J. R. Pemberton, Roy R. Morse, T. F. Stipp, John R. Roberts, R. D. Bush, Alexander Anderson, J. A. Taff, F. 0. Martin, J. E. Van Gundy, E. K. Parks, A. C. Rubel, Lew Suverkrop, W. L. McLaine, Gerard Henny, Walter Stalder, Lester C. Uren, Hoyt S. Gale, W. L. Walker. Rocky Mountain.—Fred E. Wood, chairman, J. G. Bartram, C. E. Dobbin, Wilson B. Emery, Charles E. Erdman, R. D. Hawley, E. W. Krampert, Foster Morrell, W. T. Nightingale, K. B. Nowels, C. M. Rath, Earl Shoenfelt, J. W. Steele, E. T. Wilson, J. J. Zorichak. Kansas-Oklahoma.—Committee members: C. E. Beecher, chairman, A. W. Ambrose, R. C. Hauber, Clyde Alexander, R. F. MacArthur, C. R. Swarts, M. M. Valerius, E. H. Griswold, G. 6. Rollin, L. Murray Newman, David L. Trax, Richard K. Huey, Marvin Lee, Harry Johnson; others who contributed: E. A. Carr, Paul S. Ache, K. C. Slater, R. S. McFarland, J. R. McWilliams, Joseph Chalmers, Henry A. Ley, Dorsey IIager, H. C. George, W. K. Whiteford, L. G. E. Bignell, L. E. Smith, George E. Burton. Texas, Louisiana, Arkansas, New Mexico.—Frederic H. Lahee, chairman, Donald C. Barton, C:. E. Beecher, Olin G. Bell, G. E. Campbell, Paul Wagner, John West, Robin Willis, J. M. Forgotson, E. J. Gorman, P. S. Haury, Marvin Lee, C. F. Lytle, L. H. McBee, T. F. Petty, C. C. Pope, F. S. Prout, J. C. Stewart, J. R. Suman, L. P. Teas, W. C. Thompson, A. F. Truex, R. B. Campbell, M. G. Cheney, P. C. Dean, F. W. DeWolf, Dugald Gordon, B. A. Hardey, F. E. Heath, J. F. Lucey, George C. Matson, W. H. Perot, T. W. Pew, W. A. Price, W. A. -Reiter, R. C. Stewart. Eastern United States and Foreign Fields.—H. H. Hill and E. L. Estabrook, chairmen; Dr. Richard Ambronn, Gottingen, Germany; Arthur R. Andrew,

Jan 1, 1930

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines' diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c'i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

The Bureau of Mines extends. a cordial invitation to all members of the Institute to visit Pittsburgh, Sept. 29 to Oct. 1, to participate in the dedication of the Mines Experiment Station. Accompanying this will be a nation-wide participation in a First-aid and Mine Rescue Contest. The Pittsburgh Chamber of Commerce will cooperate. The Institute will be represented by a special delegate appointed by the President. MONDAY 8:30. A. M. Bureau Building open for inspection. 10:30 A. M. Dedicatory Ceremonies in rear of Main Building, .4800 Forbes St. 2:00 P. M.. Special Train and Automobiles to Experimental Mine near Bruceton, Pa. 3 to 6 P. M. Mine Explosion and Inspection of Experimental Mine . and of Explosives Testing Plant near Bruceton, Pa. 6:00. P. M. Return by Special Train and Automobiles to B. & 0. Station, Pittsburgh. 8:00 P. M. Informal Reception and Organ Recital Carnegie Music Hall. Arranged by Carnegie Institute of Technology.

Jan 9, 1919

By B. Yarar, J. Kaoma

[Introduction The critical surface tension of wetting of hydrophobic materials has been investigated extensively by Zisman et al. (1973) and relates the spreading of a liquid on a solid to the surface tension of this liquid. Thus, the Zisman ap¬proach shows that a plot of Cos 0 versus ?LV where, 0 is the contact angle and ?LV is the surface tension of that liquid in contact with its own vapor at equilibrium, produces a straight line which can be extrapolated to Cos 0 = 1. The intercept corresponds to a given ?LV, termed the critical surface tension of wetting. In instances, however, Cos 0 - ?LV plots show deviations from linearity. Alternative approaches have also included the plotting of adhesion tension (YLV COs 0) versus ?LV that can be interpreted in terms of critical surface tension data (Lucassen-Reynders, 1963). It has, on the other hand, been customary to correlate contact angle (0) with flotation data, although it is recognized that surface inhomogeneities and related contact angle hysteresis limit the interpretations pertaining to solid surface structures purely based on contact angle measurements. It is nonetheless true that 0 = 0, when the liquid is water, corresponds to a hydrophilic solid. Determination of ?c by contact angle measurements in conformity with the Zisman approach can encounter experimental difficulties, especially when solids are in a powder form. Following the reasoning that 0 = 0 corresponds to the hydrophilic state of a solid, froth flotation experiments can be expected to produce critical surface tension of wetting values for powders. The technique that consists of plotting recovery (% R) versus YLV data and extrapolating the linear part of the curve to % R = 0, has been described elsewhere (Yarar and Kaoma, 1984). This paper describes some of the results obtained by the extrapolation technique mentioned above, using various sulfide minerals. Experimental Materials Molybdenite (MoS2), sphalerite (ZnS), chalcopyrite (CuFeS2), chalcocite (Cu2S), and galena (PbS) were handsorted from massive samples and ground by mortar and pestle, and the -147 Fan fraction used in experiments; sulfur (S) was a C.P. Fisher Scientific Co. product. Method One gram powder samples were conditioned for three minutes in methanol-water solutions of predetermined surface tension values and the percents recovered by flotation using a Partridge-Smith Cell (Partridge and Smith, 1972), were plotted against each ?LV value. Results and Discussion The percent recovery versus ?LV for two naturally hydrophobic solids, i.e., natural molybdenite, MoS2 and sulfur are given in Fig. 1 where it is seen that ?c for sulfur is obtained as 31.5 mNm-1 whereas for MoS2, it is 26 mNm-1. Figure 1 also shows that the new flotation technique described, for estimating ?c is in good agreement with the Zisman method. Curves obtained by the same method for the minerals Cu2S, PbS, and ZnS are given in Fig. 2, where it is seen that for Cu2S, ZnS, and PbS, the extrapolation to % R = 0 produces ?c values of 36, 39, and 49 mNm-1, respectively. CuFeS2, on the other hand, gives a curve that does not permit such an extrapolation to obtain a ?c value with certainty. Nonetheless, treatment of the powder with 8.95 X 10-5 molar Na2S solution followed by washing with distilled water prior to flotation effects the curves as shown in the insert of Fig. 2. The type of curves given in Fig. 1 appear to be typical of hydrophobic solids as can also be observed in Fig. 3. The composition of solid and minute quantities of inclusions seem to play an important role as regards the surface properties of solids as reflected by the slope of the linear part of the % R - ?LV plot and thus the value of ?c obtained by this technique. For example, MoS2 of three different stoichiometric compositions produced the data given below. [MoS2MoS2.14Mo1.002S2 ?c mNm-126.029.031.0 dR/d?8.95.23.0]]

Jan 1, 1985

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Jan 1, 1907

By Frank A. Herald

Through the generous cooperation of the authors of the papers in this chapter, a great wealth of fundamental data is being made available. The same plan of securing and submitting data will be carried forward next year, with the hope of making a nearer approach to complete presentation of the data contemplated in the plan. In order to conserve space, we are printing below such footnotes as have general application to Table 1 in the papers in this chapter: Footnotes to Column Headings Table I In areas where both oil and gas are produced, unless gas is marketed outside the field, such areas are included in column headed "Oil." Manufacture of casinghead gasoline and carbon black is interpreted as outside marketing of gas. Production per acre is determined by dividing into the number of barrels of oil the sum of the number of acres assigned to "Oil" plus such number of acres of the total assigned to "Oil and gas" as represents the portion thereof occupied by oil. Wells producing both oil and gas are classified as "Poducing oil only" unless gas from them is marketed off the lease. W. water; G. gas; A, air. Bottom-hole pressures are preceded by "e." All other figures represent pressures at casinghead with well closed. P, paraffin; A, asphalt; M, mixed. 0 Cam, Cambrian; Ord, Ordovician; Sil, Silurian; Dev, Devonian; Mis, Mississippian; MisL, Lower Mississippian; MisU, Upper Mississippian: Pen. Pennsylvanian; Per. Permian; Tri, Triassic; Jur. Jurassic; CreL, Lower Cretaceous; CreU. Upper Cretaceous; Eoc, Eocene; Olig, Oligocene; Mio. Miocene; Pli. Pliocene. 6, sandstone: SH, sandstone, shaly; Ss, soft sand; H, shale; L, limestone; LS, limestone. sandy; C, chalk; A, anhydrite; D, dolomite; Da. arkosic dolomite; GW, granite wash; P, serpentine. Figures are entered only for fields where the reservoir rock is of pore type. Figures represent, ratio of pore space to total volume of net reservoir rock expressed in per cent. "Par" indicates that the reservoir rock is of pore type but said ratio is not known by the author. "Cav" indicates that the reservoir rock is of cavernous type; "Fis," fissure type. A, anticline; AF, anticline with faulting as important feature; Af, anticline with faulting as minor feature; AM, accumulation due to both anticlinal and monoclinal structure; H, strata are horizontal or near horizontal; MF, monocline-fault; MU, monocline-unconformity; ML, monocline-lens; MC, monocline with accumulation due to change in character of stratum; MI, monocline with accumulation against igneous barrier; MUP, monocline with accumulation due to sealing at outcrop by asphalt; D, dome; Ds, salt dome; T, terrace; TF, terrace with faulting as important feature; N, nose; 9, syncline. Information will be found in text as indicated by symbols: A, name of author, other than above. who has compiled the data on the particular field; C, chemical treatment of wells; G, gas-oil ratios; P, proration; U, unit operation; R, references; W, water; 0. other information.

Jan 1, 1934

By D. L. Katz, M. J. Rzasa

The derivations of three methods of computing the static pressure gradients in natural gas wells have been presented to show the assumptions made. Charts were developed from which the pressure gradients may be read when the well-head pressure, the well fluid gravity, depth, and the average well temperature are given. A chart for estimating the well fluid gravity from the condensate content and separator gas gravity is included. The effect of the increased average well temperature after flow on the calculation of the static pressure gradient is discussed. Introduction Reservoir pressures have been calculated from well-head pressures for gas wells for many years. As the pressure measurements become more accurate, the need for a reliable calculation of the static pressure gradient often arises. This paper will develop the several methods for computing the pressure gradient in gas wells and make a comparison between them. The method of calculating static pressure gradients in common use is Eq. I (ref. I) or its counterpart which includes a factor for the deviation of the gas from the ideal gas law. P2 - P1 = P1(e0.0000347GX _ I) Eq. [I] in which P1 = pressure at well head, lb. per sq. in. abs. PP = pressure at bottom of well, Ib. per sq. in. abs. G = gas gravity X = depth of well, ft. An alternate method is to compute the average density of the gas in the well and multiply by the well depth in a manner similar to that used for liquid gradients. Derivation of Formulas A static pressure gradient is a special case of the general fluid-flow equation. Consider a pound of fluid flowing in a vertical column from point I to point 2, Fig. I. By an energy balance for fluid flowing from I to 2: U1 + P1V1 + u12/2g + X1 + q = U2 + P2V2+ u22/2g+X2 +W [2] in which U = internal energy, ft-lb. per lb. P = pressure, lb. per sq. ft. V = volume, cu. ft. per lb. u = average linear velocity, ft. per sec. X = height above datum, fl. q = heat absorbed by fluid, ft-Ib. pcr lb. W = work done by system, ft-lb. per lb. An energy balance on the fluid itself gives: U = ?TdS - ?PdV + etc. [3] in which T = temperature, deg- R- S = entropy, ft-lb. per deg. R. per lb.

Jan 1, 1945

By Y. C. Liu

The orientation relationship between the dejormation and recrystallization textztres of binary Cu-P alloys of high phosphorus content was observed to he a ± 14-deg (110) rotation. According to the ori-ented-gvowth hypothesis, the same relationship should exist between a successfully flowing pain and the strained single-crystal matrix of alloys of corresponding composition. The orientations of thirty successfully growing grains were obtained in a Cu-1.0 at. pct P alloy. Both a conventional analysis and the more detailed analysis advanced in the present study demonstrate that the observed orientation relationship is not comparahle to that predicted by the oriented growth hypothesis. IT has been shown experimentally that the formation of recrystallization textures in metals may be explained on the basis of the oriented-growth hypothesis. This conclusion is based primarily on the results of cooperative experiments carried out by various investigators in aluminum. Beck and HU' suggested that the orientation relationship between the recrystallization and deformation textures of aluminum is a 38-deg(111) rotation. A similar relationship, i.e., a 40-deg(111) rotation, was observed between the primary and secondary recrys-tallization textures.' Since the secondary grains result from a process of selective growth, this naturally implies that the same mechanism is also responsible for the formation of the primary re-crystallization texture from the deformed matrix. Further evidence was provided by the experiments of Liebmann, Liicke, and Massing3 and Yoshida, Liebmann, and Lucke.4 They observed that grains which could successfully grow into strained aluminum single crystals invariably exhibited the same orientation relationships with their matrix. Thus, regardless of other opinions,5'9 these results offered good evidence in favor of the oriented-growth hypothesis. In order to examine broader applications of this oriented-growth hypothesis, experiments should be carried out in metals other than aluminum. In a recent investigation on the recrystallization textures of binary copper alloys with phosphorus, arsenic, and antimony,7 it was found that the predominant recrystallization components were related to the deformation textures by a (110) rotation. The (110) rotational relationship is different from the (111) relationship generally proposed between the recrystallization and deformation components of other binary copper alloys. 1,8,9 Applying the observations made for aluminum, the oriented-growth hypothesis predicts that the orientation relationship of grains successfully growing into the strained single crystals of either one of these copper alloys should correspond to that observed in the textural study. Verification of this prediction would provide a critical test of general applicability of the oriented-growth hypothesis to the formation of recrystallization textures in fcc metals other than aluminum. The Cu-1.0 at. pct P alloy was selected in the

Jan 1, 1964

By Robert J. McKay, F. P. Huston, WILLIAM G. HUMPTON

THE manufacture of nickel-clad steel plate and the fabrication of articles from it has progressed far enough to permit a general description of the working methods used. The manufacture of sheets made up of layers of nickel and steel is not new as a sheet of this character was patented in Germany in 1893. Present development differs mainly in the size and finish of the product. The earlier light-gage highly finished products have been limited in their application due to their similarity, in certain respects, to electro-plated and highly finished alloy sheets. The new product is a relatively heavy plate 1/4 or 3/s in. thick and heavier, with one side coated with nickel, the weight of nickel being of the order of 10 per cent of the whole. The finish is that of hot-rolled steel plate.

Jan 1, 1931

By L. F. Stutzman, George Thodos

A new graphical method, which is a modification of that proposed by Buckley and Leverett', is presented for the determination of the displacing fluid saturation at breakthrough for frontal drive mechanisms. This method is applicable to all types of fluids, which may be either soluble or insoluble in the oil at reservoir and injection conditions. This adaptation has unique advantages in handling problems in which either liquids or gases are the displacing fluids. INTRODUCTION In the displacement of oil from a reservoir with water or gas injected into the formation or by the expansion of a gas cap, the determination of breakthrough or flood advance is important to define the initial and subordinate phases of the operation. Thus, the determination of the displacing fluid saturation at breakthrough is fundamental to the establishment of over-all reservoir production. Methods for analyzing this saturation and for calculating production rates have been previously reported1,'*".". All of these methods utilize the rate equation for linear flow developed by Buckley and Leverett1. xs = QT - Qn/A? (?fu/?Su) .....(1) Sp where f, represents the volumetric fraction of displacing fluid in the total flowing fluid within the reservoir as is defined by: fo = 1/1+ ku/kd µn/µn .......(2) Since the time, ?, necessary for the flood front to travel distance ?X is unknown, Eq. 1 cannot be solved directly for the determination of the breakthrough point. Therefore, it becomes necessary to solve Eq. 1 simultaneously with an equation representing a fluid bal-ance on the reservoir behind the flood front. To develop such a fluid balance equation, it has been assumed that the fluid composition is uniform in the reservoir behind the flood front. Based upon this assumption, the follow-ing equation can be derived from a material balance on the displacing fluid: x = (?X) s Dx ? x=0 [ Snx - Sn1 ] dx = QT - Qn/A? It is readily observed that the displacing fluid satura-tion behind the flood front, Snx, may be determined through the simultaneous application of Eqs. 1 and 3. Although the approach may vary, this objective re-mains the same for all of the previously mentioned graphical or analytical methods. After Sox is determined, it is then possible to calculate the gas-oil and/or water-oil ratios and the rates during the initial and subordinate phases of production, and thereby define the production history of the reservoir. In this presentation only the de-termination of Snx is considered, and the reader is re-ferred to the several texts in reservoir engineering2,4,5 for a complete discussion on the methods for establish-ing the production history of a reservoir. PROPOSED METHOD FOR DETERMINING Snx Since at any time the quantity, QT - Qn/A? is a constant, Eq. 1 may be expressed in differential form as follows: dxsn = QT - Qn/A? d (? fn/? Sn) sn .....(4) Eq. 4 may be substituted directly into Eq. 3 to obtain: ? fn/? Sn ? [ Snz - Sn] QT - Qn/A? d ( ? fn/? Sn) = QT - Qn/A? ...............(5) Eq. 5 simplifies to the expression: ? fn/? Sn ? [ Snz - Sn] QT - Qn/A? d ( ? fn/? Sn) = 1 ....(6)

Jan 1, 1958

By K. Reinhardt

The idea of burning blast-furnace gases directly in gas-engines, instead of under steam-boilers, as had previously been done, was first put into practice barely ten years ago, almost simultaneously in Great Britain, Germany and Belgium. The pioneers of this movement made their first experiments with small engines. After these experiments had given satisfactory results, and it had been shown that the thermal value of the poor blast-furnace gases, in spite of defective scrubbing, could with safety be directly transformed into mechanical work in the gas-engine, there very soon arose a considerable demand for gas-engines of large power, similar to the large steam-engines employed in metallurgical works. In face of these sudden requirements, the gas-engine builders were placed in a difficult position; for up to that time the gas-motor was considered as suitable for small engines only, and it was generally believed that the limit of size had been attained with 100 to 150 effective h.p. in a single cylinder. Manufacturers of gas-motors, however, did not underrate the advantages offered by this new field for their manufactures, and it so happened that in Germany the Berlin-Anhaltische Masch-inenbau-Gesellschaft, of Dessau, was the first to undertake the construction of a 600-h.p. two-cycle gas-engine, with two cylinders of the Oechelhauser-Junkers type, for the Hoerder Mining & Smelting Company. The engine was started in 1898, and, with a few improvements and alterations, is still working satisfactorily. This engine worked with astonishingly high effciency, considering the period. The builders were therefore

Jan 1, 1907

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

Jan 1, 1966

By F. L. Fayers, J. W. Sheldon

It has been a matter of concern to the petroleum industry to determine what effect the capillary term has on saturation profiles, since these profiles determine ultimate economic oil recovery. In their original solution of the non-capillary two-phase flow problem, Buckley and Leverett&apos; showed that solutions of the two-phase flow equations became multiple-valued in saturation. Since it is physically unrealistic for saturation to have more than one value at a given position, Buckley and Leverett resolved this difficulty by introducing a saturation discontinuity or "shock". They evaluated the strength and position of the shock from material balance considerations. Recently Sheldon, Zondek and Cardwell&apos; have demonstrated that the method of characteristics can be used to solve this and related problems. Owing to capillarity it is physically unlikely that saturation shocks occur in an oil reservoir. Buckley and Leverett suggested that the effects of interfacial tensions should be included in the fluid flow equations, if the solutions are to give continuous single-valued saturation distributions. An analogy to this problem is encountered in the theory of wpersonic compressible flow where the introduction of the viscous term eliminates shock behavior. However, the mathematical form of the capillary term in the porous medium fluid flow equations differs from the viscosity term in the Navier-Stokes equation. This paper demons~rates that capillarity does eliminate the triple-valued behavior and indicates the magnitude of capillary and gravity effects on the saturation profile for a variety of systems. DERIVATION OF LAGRANGIAN AND EULERIAN FORMS OF THE DISPLACEMENT EQUATION The equations representing capillary, two-phase flow are given by applying Darcy&apos;s law and a material balance condition for each phase. The familiar Darcy and material balance equations are as follows. ^U*^0......<3, ^^r=°......c« S is the saturation of the water phase, and B the inclination of the porous medium. Pressures in the oil and water phases differ by the capillary pressure associated with the interfacial tensions, P.-P.=pAS)..........(5) where p, is determined experimentally. The porous medium is said to be oil-wet if P, > Po and water-wet if P, < Po. If the fluids are incompressible and the total volumetric flow rate, q, is constant, then v, f v,, = q...........(6) By eliminating P.. /»,, and v, from Eqs. 1, 2, 5 and 6 it follows that It is convenient to normalize the variables in the problem after the manner of Handy and Hadley% so that Eqs. 3 and 7 become where j,, = —, the fractional flow of water; (F, is a capillary pressure normalizing constant.) Substitution of Eq. 9 into Eq. 8 gives In this partial differential equation for an initial value

FREDERICK G. BRENNEMAN Frederick G. Brenneman died of pneumonia at his home at Pottsville, Pa., on November 24. He was in the class of 1912, of the Pottsville High School, attended Bellefonte Academy, and graduated from the Colorado School of Mines, at Golden, Colo., in 1916. He is survived by his parents, Mr. and Mrs; Philip Brenneman and three brothers, Louis P. and Robert C. at home, and John :F., of Camp Merritt, N. J. Mr.

Jan 1, 1919

Arizona E. P. MATHEWSON, Chairman F. W. MACLENNAN, First Vice-chairman CLYDE E. WEED, Second Vice-chairman E.D. GARDNER, : Secretary-Treasurer Box 4097, University Station, Tucson, Ariz. ARTHUR CROWFOOT G.H. DOWELL HENRY F. EASTER R.D. LEISK Boston Meets first Monday each month, October to May, inclusive GEORGE, W. METCALFE, Chairman ROBERT S. WILLIAMS, Vice-chairman F. LEROY FOSTER, Secretary-Treasurer Rooms G-202, Mass. Inst. of Tech. Cambridge, Mass. FREDERICK K. MORRIS GEORGE A. PACKARD

Jan 1, 1934

[Mining Methods Guy N. BJORGE, Chairman CLYDE E. WEED, Vice-Chairman HARLAN A. WALKER, Secretary Alluvial Mining CLINTON BERNARD O. B. PERRY R. B. EARLING C. M. ROMANOWITZ BENERE H. GRANT J. B. STAPLER CHARLES THURMAN Open-Cut Mining Iron G. E. DIEHL P. G. HARRISON EARL E. HUNNER Copper Louis BUCHMAN W. H. GOODRICH J. H. DAVIS WALTER S. LARSH Underground Mining Iron ROY A. BOWEN S. R. ELLIOTT T. C. DESOLLAR W. A. KNOLL GEORGE H. RUPP]

Jan 1, 1940

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s&apos;S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.&apos; There are a few marked discrepancies in the intensity comparison of the two s&apos;s, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s&apos; have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955