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By Colin G. ink

OUTSTANDI'NG in progress among the less familiar 'metals during 1936 is the electrolytic production of 99.9 per cent manganese meta1 readily and many quantity. Strictly speaking, manganese should not' be classed as 'a rare metal, since there is 800 times as much manganese in the earth's crust as there is zinc or lead. But manganese' as a metal is rare, just as titanium metal is rare though titanium is five times as abundant in the earth's crust as manganese.

Jan 1, 1937

PROF RICHARD ÅKERMAN Stockholm, Sweden DR. FRANK DAWSON ADAMS Montreal, Canada PROF RICHARD BECK Friberg, Germany ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England PROF HANS HOFFER Leoben, Austria JAMES FURMAN HOEFER Leoben, England PROF HENRI LOUIS LE CHATELIER Paris France

Jan 1, 1917

PRESIDENT HORACE V. WINCHELL MINNEAPOLIS, MINN. PAST PRESIDENTS PHILIP N. MOORE ST. Louis, Mo. SIDNEY J. JENNINGS NEW YORK, N. Y. FIRST VICE-PRESIDENT A. R. LEDOUX NEW YORK, N. Y. TREASURER GEORGE D. BARRON NEW YORK, N. Y.

Jan 1, 1923

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By Donald J. Drinkwater, M. C. Fuerstenau

Many important contributions to the more fundamental aspects of mineral processing have been made this past year. Mular1 researched the flotation characteristics of pure zinc oxide and also samples that had been doped with Al+++ and Cu++. Correlation of the response of pure zinc oxide to oleate flotation with a calculated zpc (from solution equilibrium) suggests that adsorption of oleate ion is coulombic in nature. Doping the sample with Al+++ (which will make the ZnO more n-type) had a marked effect on the maximum value of pH at which 50% recovery was obtained at constant collector addition. That is, when 0.5 mole percent Al+++ was added, the pH for 50% recovery was reduced by about four units. Treatment with Cu++ was found to have little effect on the flotation response of zinc oxide, even for additions of one mole percent. Since the zero points of charge of the Al+++ doped powders were not measured, it was not possible to correlate flotation data of these samples directly with charge phenomena.

Jan 2, 1966

By Wayne C. Hazen, James K. Kindig

As the complexity of hydrometallurgical systems increases, it offers new opportunity for applications of solvent extraction. However, the high capital cost of mixer-settlers for large flow rates is a drawback to wide application in base metal recovery. This paper presents information on the use of cyclone separators in place of settlers with attendant significant reduction in capital cost. Various flowsheet possibilities for this development are discussed.

Jan 1, 1972

NEW MEMBERS The following list comprises the names of those persons who became members during the period Dec. 10, 1916 to Dec. 31, 1916. BOWMAN, Joseph V., Chem., Andes Copper Mining Co., Chanaral, Chile, South America. CALDER, NORMAN L., Min. Geol., Cia. Minera y de Fomento, Watkins, Fomento Prov. de Santa Clara., Cuba. CONRADS, RALPH A., Met. Engr., Magna Plant, Utah Copper Co., Garfield, Utah. FARR, T. H. POWERS, JR. Asst. Assayer, Argonaut Mining Coy Jackson, Cal HAURY, PETER S., Min. Engr ...Alta Loma, Cal. HOULE, ARTHUR, Supt., Shattuck-Arizona Copper Co., Box 2009, Bisbee, Ariz. LEIB, VICTOR E?, Min. Engr 4204 Ave. D, Austin, Tex. LINDSLEY, THAYER, Min. Engr 82 Beaver St.,. New York, N. Y. POTTER, OCHA Supt., Superior Copper Co., Houghton, Mich. ROCCA, BERNARD T.; Engr., Bluebell Mine, Cons. Arizona Smelting Co., Mayer, Ariz. SAFFOLD, RAY P P.'0. Box 436, Douglas, Ariz. THOMS, JAMES EZRA, Asst. Chief, Milling, -Roasting, Acid Depts., Mineral Point Zinc. Co., Depue, Ill. TOMITA, HARUYOSHI, Met. Engr., Mitsubishi Co., Osaruzawa Mine, Akita-ken, Japan.

Jan 2, 1917

By George J. Young

(Cleveland Meeting, October, 1912.) I. GENERAL. THE recurrence of mine-fires in Nevada during the past decade is not only a matter of interest, but also one of considerable concern to engineers and mine-managers. The more important fires may he enumerated as follows: Forman Shaft fire., Gold Hill, April 21, 1903 ; shaft-house, machinery, and shaft, destroyed; loss estimated at $50,000.; Cause Unknown. Union Shaft fire, Virginia City, July 14, 1904; shaft-house, machinery, and shaft in part destroyed; loss estimated it $100,000; cause of fire stated as the careless throwing of a match in the rope-house. Sutro Tunnel fire, Virginia City, Jan. 27, 1909 ; 700 ft. of tunnel-timbering destroyed, and direct damage of $10,000; cause ' probably electric wires." Belcher Shaft fire, Gold Hill, Aug. 9, 1910; shaft-house destroyed, machinery ruined, and upper part of shaft damaged; damage, $25,000; no cause given. Belmont Mine fire, Tonopah, Feb. 23, 1911; fire started in winze ; 17 men killed. Giroux Mine fire, Kimberly, Aug. 23, 1911 ; fire originated iii shaft-station from unknown cause; 7 men killed, and $34,¬521 damage caused. (NOTE 1.-On June 11, 1912, some time after the present paper was written, a fire broke out in the pump-room on the 2475 station of the Ward shaft, Virginia City. This fire was caused by the short-circuiting and exploding of the starting-switch on No. 5 pump. The oil in the switch was scattered about and set fire to the timbers and laming of the pump-room. The pump-roan in charge notified the surface, and the * Professor of Mining and Metallurgy, Mackay School of Mines.

Oct 1, 1912

US Tin Mission To Study Costs in Far East A move to obtain adequate supplies of tin at prices the United States is willing to pay was initiated when the interagency tin mission left for the Far East. The Mission, which includes representatives of the Reconstruction Finance Corporation, State Department, Defense Minerals Procurement Agency and the Bureau of Mines will go to Indonesia and Malaya. The primary purpose of the mission, according to officials, will be to study tin production costs, not to negotiate for the purchase of tin. The mission will be prepared to enter into negotiations, if the Far Eastern producers are amenable. The United States withdrew as a large-scale buyer of tin some months ago in protest against what it considered exorbitant prices being charged in the Singapore market. Subsequent attempts to negotiate for a steady tin supply at what this country considers reasonable prices have been unavailing. The U. S. is prepared to enter into a two or three year contract with the price of tin somewhere between $1.00 to $1.12 per lb. The decision to abstain from the market has not yet put a squeeze on U. S. supplies. Substantial quantities of tin still are coming in from Malaya under an old contract.

Jan 12, 1951

By Joseph B. Darby, Paul A. Beck

IN isothermal sections of several ternary systems, the a-phase was found1 to extend in the form of a relatively narrow elongated field, connecting the U-phases that are present in the adjoining binary systems. This was interpreted in accordance with the conception that the U-phase is an electron compound and the ternary U-phase fields were shown in several systems' to extend approximately in the direction of constant average d-shell electron vacancy number per atom. ' However, in the various isothermal sections of the Fe-Cr-Mo system" the ternary a-phase field was

Jan 1, 1958

By AIME AIME

EITHER the 2300 people who came to the Annual Meeting were in a better frame of mind or they were resigned to their fate, or it was a better meeting than usual. Whatever the reason, at the 1nstitute?s 148th meeting the attendance was better than ever before, things went more smoothly than in some previous years, and complaints appear to have been almost entirely absent. Patience was sometimes reauired but. almost without exception, it was forthcorning the well-known recession seems to have given many members enough leisure time to come to the meeting without depriving them of the tangible wherewithal to come.

Jan 1, 1938

C. A. HANSEN (communicated appendix*).-Since the above paper was written, tests have been conducted with a view to securing a sounder basis for discussing the effects of temperature on the behavior of the zinc cell. The following data, while making no pretense to great accuracy, are still reasonably close. Cells were operated with the same feed solutions, but at varying temperatures, the latter being controlled by means of immersed steam coils. Current efficiencies obtained indicate that the corrosion rate

Jan 11, 1918

By H. Rees

This paper supplements and brings up to date a report prepared earlier this year and presented at the Eleventh Pan American Railway Congress in Mexico City. Most of the original report is contained in this paper in order to acquaint the reader with the project background. On December 1, 1961, construction of this locomotive was completed. Stationary testing started immediately, and a host of problems in various areas were uncovered. Many of these had no relation to the use of coal in a direct fired gas turbine. All of them emphasized the problems which plagued previous projects of this kind. In 1944 the Locomotive Development Committee of Bituminous Coal Research, Inc., was formed to study the problems of combustion, coal handling, and fly ash removal which would have to be solved before coal could be used to fire a gas turbine. By 1947 this committee was composed of the chief executive officers of nine eastern railroads and five eastern coal companies. All of the members of this committee were vitally concerned in a coal fired gas turbine because coal cost only one-fourth as much per heat unit as fuel oil. A number of research projects were started to develop and test components on a small scale. This included work at John Hopkins University, Battelle Memorial Institute, Institute of Gas Technology at Chicago, Purdue University, and Southern Research Institute. By 1946 a pilot plant had been installed at the Dunkirk, New York plant of Alco Products Div. of American Locomotive Co. The U. S. Bureau of Mines made available to the Locomotive Development Committee (hereafter called LDC) a Houdry process gas turbine plant, originally destined for a Russian oil refinery. The full scale pilot plant was used to evaluate the results obtained from the small scale studies under actual gas turbine conditions. Operation of this plant disclosed a number of problems which had not been discovered in the small scale tests. By 1951 four 250 hr tests had been conducted with the Houdry gas turbine to test out a variety of equipment. The major problem concerned the removal of abrasive fly ash from the products of combustion so that wear on turbine blades would not be excessive. The first 250 hr test showed that the original fly ash separating equipment was inadequate. Large ash particles passing through the turbine blading were nicking the leading edges of the first row blades. At the conclusion of the second 250 hr test, erosion was so severe that the first row of stator and the first row of rotor blades were replaced. At the end of the third 250 hr test, it was necessary to replace the first three rows of stator blading. The fourth test was used to test out a new design fly ash separator developed by LDC and named the Dunlab tube. This device gave more encouraging results than any of the others tested. Early enthusiasm for overcoming major difficulties had resulted in placing an order in 1946 with Allis-Chalmers Mfg. Co. for a 3750 hp regenerative gas turbine. The gas turbine, together with associated combustion and ash removal equipment, coal handling equipment, generators and gear reduction unit was installed at Dunkirk by 1951. A 750 hr test was made in 1952 with the LDC-Allis Chalmers gas turbine power plant. At the end of this test it was necessary to replace the first four rows of both rotor and stator blading. Rows 5 and 6 did not require replacement. In 1953 the American Locomotive Co. joined with LDC and assumed an active role in equipment development and manufacture. During 1954 LDC-Alco operated the rebladed gas turbine 300 hr to determine if a new fly ash separator was adequate. Performance of the improved separator was considerably better, but trouble was experienced with clogged blowdown lines from the Dunlab tubes. When these lines clogged it permitted the passage of abrasive particles. In 1955 a total of 1421 hr was run. This included 243 hr of cycle operation on Union Pacific coal from the D. O. Clark mine at Superior, Wyoming. During the 243 hr a total of 370 tons of coal was consumed. The purpose of this test was to determine if U.P. coal was suitable for use in a coal fired turbine. It was the unofficial opinion that it was as good or better than the eastern coals that had been tested.

Jan 1, 1964

By Fred C., Bond

DETERMINATIONS of circulating load in a classifier operating in closed circuit with a grinding mill are usually made from screen analyses of the mill feed and classifier products. The percentage remaining on someone selected screen size must be used in the calculation, and, because of the wide variation in average particle size between the mill feed and classifier overflow, an accurate and representative result at the selected mesh is often difficult to obtain. To overcome this difficulty and reduce the time required in making the determination, I have devised a method which uses the liquid-solid relationship in the circuit rather than screen analyses. The quantities required for the calculation include only the usual dilution and feed tonnage measurements, which should be made regularly in the course of ordinary mill operation and, in addition, the amount of new water added to the classifier, or to the head of the mill with the new feed. If measurements are obtained on both of these quantities it is possible to check the calculated circulating load, and to calculate the percentage of moisture in the new feed to the mill; or, if the latter is known, to check the feed tonnage.

Jan 1, 1937

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By S. C. Termes, R. L. Wilfong

As part of an effort to provide basic data on the fundamental scientific and engineering principles of minerals beneficiation, the Bureau of Mines is conducting research on the flocculation of mineral fines. This paper presents results of studies using cross-linked starches containing carboxyl, diethanolamine, iminodiacetic acid, and xanthate groups to flocculate hematite, goethite, chromite, manganite, pyrolusite, cuprite, and cassiterite fines. The carboxyl and xanthate derivatives flocculated all minerals except cassiterite; the latter was flocculated by only the diethanolamine derivative. The imlnodiacetic acid derivative flocculated hematite, goethite, chromite, cuprite, and pyrolusite fines. Zeta potential measurements were made to help define the reaction mechanism responsible for flocculation. These measurements indicate that electrostatic attraction probably is not involved, except possibly in the case of the diethanolamine derivative. The separation of hematite from quartz by selective flocculation with chelating crosslinked starches under two pH conditions and with two dispersing agents is described. Best recoveries and grades were found when either the carboxyl or xanthate derivatives was added at the natural pH of the pulp in the absence of a dispersing agent.

Jan 1, 1984

By J. C. M. Li

The steady state shape of a shrinking cylindrical grain boundary of miform boundary energy is shown to be circular. This is based on the principle of either the minimum rate of entropy production or the minimum thermokinetic potential. The circular shape corresponds also to a state of minimum (not maximum) velocity. The steady state shape of a grain boundary moving between two inclined surfaces is a circular cylindrical arc whose position and curvature will be afjected by the nature of the surfaces. The minimum thermokinetic potential is the only valid criterion in this case. THE preceding paper1 reports an interesting experiment in which it is shown that a grain boundary moving between two inclined surfaces assumes a circular cylindrical arc whose axis nearly coincides with the line of intersection of the two surfaces. The driving force is well defined since it is the energy of the grain boundary itself. The velocity of the grain boundary is found not to vary linearly with the driving force. Several interesting questions arise: 1) What principle determines the shape of a moving grain boundary? 2) What is the effect of the inclined surfaces? 3) How do we understand the nonlinear velocity-driving force relationship? It is attempted in this paper to discuss the first two questions based on irreversible thermodynamics and in a following paper to discuss the third question based on dislocation theory. STEADY STATE SHAPE OF A SHRINKING LOOP (A CYLINDRICAL GRAIN BOUNDARY) In irreversible thermodynamics, there are two criteria for the steady state. One is the minimum rate of entropy production2 which is based on the symmetry of phenomenological coefficients and is applicable to linear force-flux relations with constant coefficients. The other is the minimum thermokinetic potential3 which is based on the integrability of a certain Pfaffian differential equation and is applicable to nonlinear systems with variable coefficients. In the case of a shrinking grain boundary loop (a two dimensional version of a cylindrical grain), the flux of atoms across the grain boundary can be taken as the local boundary velocity v measured perpendicular to the boundary (the number of atoms transferred per unit area per second is equal to the product of atom density and the velocity of the boundary). The local thermodynamic driving force can be taken as y/p with y being the grain boundary energy (invariant with respect to the orientation and curvature of the grain boundary) and p being the radius of curvature. Such driving force can be understood by considering the loop as an elastic string with tension y. As shown in Fig. 1, across a length ds along the loop, the direction of y changes by an angle d@ which is ds/p. Because of this change of direction, the tension exerts a force perpendicular to the curve equal to yd@. The force per unit length is then y/p. According to the experimental observation, the velocity v is a power function of y/p, where M is the velocity at unit driving force and 'n is a constant. The rate of entropy production per ds along the loop is vyds/pT, where T is the temperature. For a given length L of the loop, the total rate of entropy production is The thermokinetic ptentia13 has only a differential definition and its existence depends on the integrability of this definition. In this case, Eq. [3] happens to be a total differential and the thermokinetic potential can be defined as which turns out to be the same as the rate of entropy production, Eq. [2], except for a constant factor n + 1. Strictly speaking, since the flux-force relation is not linear, the rate of entropy production may not be a minimum at the steady state. However, because of the proportionality between Eqs. [2] and 141, the state of minimum thermokinetic potential happens to be the same as that of minimum rate of entropy production. The steady state shape thus can be obtained by minimizing either integral [2] or [4] for a given L.

Jan 1, 1970