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By John Chipman, Carl F. Floe

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By Carl F. Floe, John Chipman

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By R. E. Ogilvie, H. C. Gatos, R. E. Hanneman

The ejj-ect of high pressures on chemical inter-diffusion in the Fe-V system was determined by analyses of concentration vs distance profiles of atmospheric and high-pressure diffusion couples. Diffusion data were obtained as a function of tern -perature and composition. Activation energies, activation volumes, and frequency factors were determined at 1 atm, 20 kbars, and 40 kbars as a function concentration in the a and y phases. The A great deal of research has been carried out in the measurement and understanding of binary chemical inter diffusion in solids. Studies of the effects of high pressure on interdiffusion in binary systems, however, have been virtually nonexistent until the present work. This paper gives a detailed account of the effect of high pressure on interdiffusion and the Kirkendall effect in the Fe-V system. The present data are compared to existing theo- Kirkendall effects were measured at 1 atm and 40 kbars. At 1 atm Dy > DFe at the marker concentration; however, Dv approaches DFe under pressure, and at 40 kbars the values are approximately equal. The high-pressure and atmospheric diffusion data are evaluated on the basis of theoretical models. Chemical analyses of the diffusion -couple profiles were made using an electron microbeam probe. retical treatments of pressure dependence of diffusion which are based upon self-diffusion studies. THEORY The rates of atomic migration in metals and alloys are regulated by the repulsive forces exerted on an atom during its motion from one equilibrium lattice site to another and by the availability of a jump site. Application of high pressure is expected to decrease diffusion rates because it decreases interatomic distances as well as defect concentrations. A number of theoretical treatments have been focused on the problem of calculating self-diffusion coefficients in solids under atmospheric pressure. In general, the vacancy mechanism of diffusion appears to be dominant at high temperatures in most metallic systems. The migration of an atom by this

Jan 1, 1965

By W. H. Adams

At the present time all the larger and better chemical works of Europe and the United States have introduced, as essential factors in the economical manufacture of sulphuric acid, both Glover towers and Gay-Lussac absorbing columns. The clear exposition of facts given by Bode and Lunge in their very valuable technical contributions since 1870 has slowly but surely brought about radical changes from the old methods of manufacture ; but while the Gay-Lussac column has been known since 1827 and the Glover tower was originated in 1869, yet no theoretical treatise covering the subject fully was given to the world until 1876, when the various contrivances for demonstrating nitrous vitriol were described and criticized by Fr, Bode in a paper "On the Glover Tower" which obtained the great prize of the Berlin Society for the Promotion of Industry.*

Jan 1, 1887

By A. Madrazo

The Standing-Katz method for predicting liquid densities of reservoir fluids has been tested using experimental data of 154 bottom-hole or recombined reservoir fluid samples. New pressure- and temperature-correction curves for the Standing-Katz type correlation are presented which improve the accuracy of prediction. INTRODUCTION The present study was undertaken to investigate the known methods of determining liquid densities and to select one of them which might yield a better correlation if additional data were employed. An appropriate correlation would incorporate the following characteristics: (1) ease of handling in the computations, (2) results within engineering accuracy and (3) data easily accessible. After careful investigation of the different methods, the Standing-Katz correlation1 appeared to have these characteristics. The Standing-Katz correlation for liquid densities of hydrocarbon systems is based upon limited data. The original work, which employs apparent densities for methane and ethane, was based on data of 15 saturated crude oils in equilibrium with natural gas. Therefore, a test of the correlation using additional experimental data would serve either to validate the Standing-Katz correlation or to form a basis for corrections if such were necessary. PROCEDURE AND GRAPHICAL SOLUTION The data of 154 bottom-hole or recombined reservoir fluid samples were employed to calculate the densities at 14.7 psia and 60°F by the method described in Table 1. Volume contributions for methane and ethane were assigned from the pseudo liquid density plot (Fig. I), but volume contributions for N2, CO2 and HzS were not considered. The densities computed at reference conditions of 14.7 psia and 60°F were then elevated to their respective temperatures and pressures by the use of the correction curves proposed by Standing.' The percentage differences between the experimental values and the calculated values were determined; these samples were grouped into temperature, pressure and density ranges to determine a possible trend. It appeared that, at temperatures above 160°F, the calculated density values were consistently larger than the experimental density values; however, no obvious trend was found for the density and pressure ranges. There is a relationship between the pressure-correction and temperature-correction curves. This relationship, embodied in the temperature-correction curve, can be expressed as follows. The experimental densities of 125 samples above their bubble points were known. From these isothermal data, it was possible to determine an experimental-density difference between two pressures; and (from Fig. 2*), a calculated density difference between the same two pressures was determined. The relative effect of temperature must be considered in the calculated-density values. The effect of temperature can be determined by entering Fig. 3* at the two densities in consideration and obtaining the change in density at constant temperature. This change, or delta density, must be added

By JESSE L. MAURY

DEVELOPMENT of new gold mines in Canada since the price of that metal was increased in 1932 and 1933 has been of interest and importance to many of us. The day-by-day story has given an impression of aggressive effort and enough good luck so that the spirit of enterprise has been encouraged. It is the purpose of this article to report the results of a statistical appraisal which give emphatic numerical confirmation to this impression, together with certain side lights on the costs of development and equipment of new mines. The data presented have been taken from all readily available published sources up to the close of 1938 and are representative of that year. A. B. Bower did a large part .of the spadework and Weston Thomas offered many helpful suggestions.

Jan 1, 1939

By G. W. Toop

In a recent publication,31 Darken has derived an equation to describe thermodynamic behavior in ternary metallic solutions with compositions near pure component 1: Eq. [I] is understood to be a general equation, consistent with the ternary Gibbs-Duhem equation, which is proposed as a logical formalism in view of observed behavior in some binary metallic solutions31'32 rich In Eq. and am are constants obtainable from the 1-2 and 1-3 binaries. The parameter 023 may be determined from measurements on the ternary The purpose of this discussion is to compare Eq. [I) or [3] with other ternary formulations involving binary terms, within the regions of validity of Eqs. [I], [2], and [3]. First, the ternary point is considered to be at the intersection of two composition paths, one with constant N1 and another with constant N2/N3 as shown in Fig. 10. The terms in Eq. [3] may be related to the binary points shown by multiplying the first term on the right-hand side of Eq. [3] by N2 (1) /l -N1, the second term by the third term by and the fourth term by each multiplier being unity: It should be noted here that no suggestion has been made that either the binary or the ternary systems form regular solutions. However, Eq. [5] and hence Eq. [3] shows that the contribution made to the ternary excess free energy from the 1-2 and 1-3 binaries has the same form as for a regular ternary system.1 Before considering the term a23 for the above case, a second geometrical relationship is examined with the ternary point at the intersect ion of three composition paths with constant N1/N2, N2/N3, and Nl/N3, respectively, as shown in Fig. 11. For this geometry, ternary values of NZ and N3 in terms of the binary values shown may be substituted into Eq. [I]. Then by making use of identities of the form Eq. [6] contains terms that are similar to those in a ternary regular solution formulation34 based on the geometry shown in Fig. 11. Although at finite concentrations, unless the 1-2 and 1-3 binaries form

Jan 1, 1968

WE the undersigned, being all persons of full age and citizens of the United States, and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I. of said law, the existing unincorporated association known as American Institute of Mining Engineers, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows: I. That the American Institute of Mining Engineers is an unincor¬porated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals-and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publi¬cations among its members and associates the information thus obtained. II. That the persons duly appointed or designated to manage the affairs of said association are designated by the rules thereof Members of its Council; that the undersigned are all members of said Council as the same was constituted on the 29th day of December, 1904. III. That on said last-mentioned date a regularly called meeting of said association was held at its office in the Borough of Manhattan, City of New York; that thirty days before such meeting notice of the intention to incorporate said association was given by mail to each member thereof whose residence or post-office address is known; that at said meeting the following resolutions were offered, seconded and duly adopted by the unanimous vote of all its members then present, to wit: "Resolved, That it is the sense of the members and associates of the American Institute of Mining Engineers in general meeting assembled that it is desirable and necessary for the well being of said association and its members and for the furtherance of the objects for which the same has been formed, that said association incorporate under the Membership Corporations Law of the State of New York;

Jan 1, 1923

By J. E. Metcalfe

Proceedings of the Fourth Empire Mining and Metallurgical Congress, Great Britain 1949. Part II published at the Offices of the Congress in London, England, 1139 pp. The price of these proceedings is £ 2. The parts may be purchased separately at a cost of £ 1 each.-Part I of this book covers a report of the organizing committee, the inaugural meeting and presidential address, banquet at Guildhall, welcome by Sir Richard Livingstone at Oxford. and final session. Technical session and papers are also covered in Part I. Part II covers such topics as coal, present-day trends in mineral dressing and metallurgy. Mining Engineer's Survey Manual. By J. E. Metcalfe. Published for "Mine & Quarry Engineering" by Electrical Press, London, 1951. 341 pp., illus., charts, diagrs., tables, 8 ¾ x 5 1/ in., cloth, 30s., available from Percival Marshall & Co., Ltd., London, and British Book Centre, 122 East 55th St., New York 22, N. Y. Beginning with a brief treatment of surveying fundamentals and a discussion of the correlation of surface and underground surveys, this practical manual continues with descriptions of surveying practice both above and below ground including stopes, inclined shafts; etc. Space is devoted to sampling and valuation, geological considerations, and descriptions of modern surveying instruments. The organization of survey operations is covered in the last chapter.

Jan 1, 1952

By J. L. Gillson

The big mass of anorthosite in the Lake Sanford district and the bodies of titaniferous magnetite that occur in a small area near the south margin of the mass have been described repeatedly, and the puzzling problems of the genesis of the rocks and ores have stimulated the deductive reasoning of geologists for a hundred years. Some of these men have taken a leading part in describing the anorthosite rock and forming hypotheses concerning its origin; some have contributed most to the study of the ore deposits; and some have made classical Studies introducing a basic approach to the problems of the anorthosite rock and genesis of the titaniferous magnetites. Much of the writing on the problems of rock and ore genesis has been based on physical-chemical reasoning rather than on field and microscope observations of the rocks and ores. Most of these geologists conclude that the anorthosite was formed by true magmatic crystallization, involving previous settling or squeezing out of ferromagnesian minerals from the parent magma. The associated gabbro is a separate segregation or later intrusion, and the lighter colored and finer grained facies of the anorthosite is either a chilled border zone of the anorthosite or the result of granulation by crushing of the coarse, dark blue rock of the main mass. This blue rock, called the Marcy type, is named after the highest peak in the range. The finer grained and lighter colored rock is called the Whiteface, after another mountain appropriately named for a cliff colored by this facies of the anorthosite.

Mar 1, 1956

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.' Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

By W. G. Sinclair

The wartime momentum of exploration continued throughout the year 1945 despite the end of hostilities in mid-August. The table below illustrates drilling activity in the various categories: Completed wells. . . . . . . . . . . . . . . . . . . . . . . . 401 Wildcats.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104 Wildcat discoveries, oil.. . . . . . . . . . . . . . . . . . . 2 Wildcat discoveries, gas-condensate.. . . . . . . 4 Development wells.. . . . . . . . . . . . . . . . . . . . . .297

Jan 1, 1946

By J. C. Irvine

Meramec Mining Co., a joint venture by Bethlehem Steel Corp. and St. Joe Minerals Corp., is engaged in the mining, concentrating, and pelletizing of iron ore from the Pea Ridge mine near Sullivan, Mo., about 70 mi southwest of St. Louis. The orebody lies under about 1300 ft of sediments. It is tabular, about 2600 ft long and up to 600 ft thick, and lies in an approximate east-west delineation. The orebody dips about 80"s and is of unknown depth. The ore is primarily high grade magnetite with smaller zones of specular hematite. The Precambrian wall rock is rhyolite porphyry. The mine is serviced through two concrete-lined shafts, 19 ft 1 in. diam and 2500 ft deep. No. 1 shaft, equipped with an "A" type head-frame and conventional cylindrical drums, hoists men, materials, and waste rock; it is also the downcast air shaft. No. 2 shaft utilizes tower-mounted friction hoists to handle the two production skips, each with 24-ton counterweights, and a small man cage. The mine exhaust passes through this shaft. Ore is principally mined by sublevel stoping,

Jan 9, 1972

Mining and Metallurgical Society of America, 76 Beaver St., New York, N. Y. Percy E. Barbour, Secretary and Treasurer. This Society issues Bulletins each year containing papers presented, and accounts of Society business. The Bulletins each year are collected in a volume as the Proceedings for that, year. In 1931 Bulletins numbered 216 to 222, inclusive, were issued in the Proceedings for that year (vol. 24). In addition to the Bulletins two special volumes have been published: International Control of Minerals, $1; and World Survey of the Zinc Indusry, $2.25. A selected list of paper,,-from the last two volumes of the Proceedings: Vol. 24 (1931) : Bull. 216 The cycles of prices of non-ferrous metals, by L. Vogelstein; 218, Marketing problems, by T. M. McNiece; 222, Copper tariff number (a discussion of the copper tariff by a number of authors). Vol. 23 (1930): Bull. 208 to 215, inclusive: Bull. 208, Some aspects of the copper industry, by L. C. Graton; 209, The ethical question of developing Soviet mines; 213, Legal recognition of geophysical prospecting, by A. H. Rogers; The evolution of the metal cartels, by L., Domeratzky and L. Vogelstein; 214, Geological justification for "exploration permits," by L. C. Graton; 215, The future of nickel, by A. J. Wadhams.

Jan 1, 1933

By Paul A. Farrar, Felix Ermains, Harold Margolin

The systems Ti-Crand Ti-Vhave been reinvesti-gated in the region up to 40 wt pct alloying addition using both conventional and rapid quenching techniques. The Ti-Cr eutectoid temperature was determined to be at 667° & 10° C and 14.5 wt pct Cr. The solubility of the Cr in a Ti was found to be less than 1 pctat 700"C. The P transus of the Ti-V system was found to be depressed to 510°C at 40 wt pct V and the solubility of V in a Ti was found to be less than 2 wt pct at 700°C. Investigation by a. d. McQuillan1-3and m. k. McQuillan4 on the systems Ti-Co, Ti-Cr, Ti-Cu, Ti-Fe, Ti-Mn, Ti-Ni, and Ti-V has cast doubt as to the position of the ß/a + ß boundaries in many of these systems. Their investigations were carried out using hydrogen pressure and/or rapid quenching experiments, as opposed to the conventional quartz capsule techniques employed by most other investigator.'" By these methods, the ß/a + ß boundary was found to be lower than that obtained by conventional techniques in all except the Ti-Fe system. In the latter, the ß/a + ß boundary was essentially the same as the boundary obtained by conventional technique.7' On the basis of rapid quenching results in the Ti-Cr system, M. K. McQuillan4 placed the eutectoid temperature below 550°C whereas other investigations using conventional techniques had placed the eutectoid variously as between 650' and 700°C,5 between 675' and 700°C,6 between 650" and 675°C,7 at 670°C,8 and above 625"C.la9l3 In order to check these results, a reinvestigation of four of the systems was undertaken using both conventional and rapid-quenching techniques. The Ti-Fe and Ti-Mn systems will be dealt with in anoth er paper, with only the Ti-Cr and Ti-V systems being discussed here. EXPERIMENTAL TECHNIQUES Alloys employed for the delineation of the systems under investigation were prepared from iodide titanium sheet capsules containing the alloying materials,

Jan 1, 1962

The object of crushing and grinding for leaching is obviously to permit contact of the solvent and mineral and subsequent removal of pregnant solution in a reasonable time. Heap leaching is the leaching of ores that have been mined and transported to prepared, relatively impervious pads for leaching by sprinkling or ponding, and percolation of the lixiviate through the ore. Dump leaching is the leaching of dumps or low-grade ore or overburden without the use of prepared pads under them. Run-of-mine material, e. g., low -grade ore from open pit stripping operations, may be leached without crushing, and a fairly high recovery made by heap leaching. An alternate method for better grade gold/silver ores is to crush to 9 to 13 mm (318 to112 in. ) size for pad heap leaching, as used by Smoky Valley Mining Company at Round Mountain, Nevada, on gold ore, and to 38 rnrn (1 -1 12 in.), which will be done by Candelaria Partners, at Candelaria, Nevada, on silver ore. Heap leaching of copper probably began at Rio Tinto, Spain, about the year 1752. This was done by the leaching of weathering piles of ore in the open air followed by iron cementation of the liquor that drained off the heaps. Its application to the low -grade southwestern United States copper ores was overlooked for many years, and low- grade ores from Sacramento Hill at Bisbee, Arizona, were the first to be heap leached in 1923. Site preparation used a half century ago is the same today. "The need for some form of waterproofing of the pad was evident. Before leaching ore was piled, the site was cleared of cactus and brush. After clearing a gentle sloping area, it was then covered with a blanket of rolled and tamped clay or slime tailing. When heaps are built, a layer of coarse fragments may be put down first to assist drainage. A second method of leaching without grinding, usually for higher grade ores, is by vat or tank leaching of material crushed to 9 to 13 mm (318 to 112 in.) size. Such a plant is considerably more expensive than a heap leaching installation but much less costly than grinding for agitation leaching, and a recovery higher than that obtained by heap leaching is to be expected. Vat leaching has been widely used by the copper industry on higher grade copper ores but has been used in only a few small operations on that size gold or silver ores. However, such a plant should be considered for a modest tonnage of a few million tons, 3 to 7 g per mt (0.10 to 0.20 oz per st), of Carlin-type leachable ores crushed to 9 mm (318 in.).

Jan 1, 1981

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By J. H. Henderson, R. J. Wygal, J. Naar

Experimental work is reported which shows that consolidated rocks and unconsolidated porous media exhibit different imbibition flow behavior. At a given saturation the imbibition nonwetting permeabilities for a rock are smaller than the drainage permeabilities. The contrary happens for unconsolidated aggregates — imbibition nonwetting permeabilities are larger than drainage ones. A similar difference is observed for the wetting phase. Imbibition permeabilities are larger than drainage ones for a consolidated rock but smaller than drainage permeabilities for an unconsolidated medium. The results of these differences are examined for two cases. 1. Flooding Efficiency — Craig's1 scheme for the computation of production history of a five-spot water flood is shown to agree extremely well with experimental results obtained when using a system packed with glass spheres if imbibition relative permeability curves are used. 2. Alcohol-Slug Displacement — Published theory 2 on oil displacement by alcohol slugs has been questioned despite the apparent agreement between predicted and observed results. The present work suggests that, if imbibition relative permeability curves characteristic of the unconsolidated media used in the early experiments had been available to make the predictions, the inadequacy of the theory would have been immediately evident. The experimental work shows that poorly consolidated formations tend to behave like unconsolidated media. Finally, it is shown that the difference in imbibition behavior is directly related to pore-size distribution and cementation. PART 1 — THE FLOW BEHAVIOR OF UNCONSOLIDATED AGGREGATES Experiments on scaled models of field reservoirs are useful for studying new displacement processes which are incompletely understood. Even when a mathematical description is possible, the solution might be difficult and complex. An answer obtained from a scaled model is extremely valuable in such cases. A great amount of work$-5 therefore, has been devoted to the derivation of scaling laws. Similarity groups have been defined which assume (1) that the relative Permeability curves of the prototype and the model are the same whether the displacement is an imbibition or a drainage process and (2) that there is a linear relationship between the capillary pressure of the model and the prototype. For practical reasons (simplicity in the preparation of models, duration of the experiments, etc.), the porous media of laboratory models are usually unconsolidated packs of sand or glass particles. Hence, unless the capillary and flow characteristics of unconsolidated and consolidated systems are identical, the model data are applicable only to unconsolidated formations. The usefulness of scaled-model studies may then be seriouslyrestricted since most oil-bearing sands are consolidated. Perkins and Collins6 suggested the use of model and prototype curves normalized with respect to both relative permeability and saturation to improve compliance with scaling criteria. Even this technique does not give a satisfactory model-prototype match. This paper reports an observation of two-phase flow in unconsolidated sands which shows that, for most displacements, "scaling" in the strict sense of the word is not even qualitatively feasible with a sand model. It provides, however, a firm foundation for testing a theory by matching it with observed performance of laboratory-size models. EXPERIMENTAL AS a part of a basic study of packed aggregates, the relative permeability of glass-spheres and sand-grain packs was measured with capillary control. The fluids were oil and air' The spheres were packed in plastic cylinders 1-in. in diameter;

By W. J. Millard

It is well known that the excellent mica from Brazil played a most vital role in World War 11. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the united' States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. Type of Deposit Favorable The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than 1: 3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. The Economics of Stripping When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run 11 per cent good stain and better when trimmed and contain 2 kg, of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should be used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.14 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.15. To this should be

Jan 1, 1948

By W. J. Millard

It is well known that the excellent mica from Brazil played a most vital role in World War 11. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the united' States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. Type of Deposit Favorable The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than 1: 3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. The Economics of Stripping When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run 11 per cent good stain and better when trimmed and contain 2 kg, of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should be used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.14 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.15. To this should be

Jan 1, 1948