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By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By R. F. Evans, J. M. Avery

MUCH has been written of the glamour of magnesium from sea water, the Aladdin-like creation of a huge magnesium plant in the Nevada desert using cheap hydroelectric power from Boulder Dam; the marvels of the Hansgirg process for the electrothermal reduction of magnesium oxide by carbon, and the ferrosilicon process for producing magnesium from dolomite. This is the story of the production of -magnesium by the electrolytic process, using steam-electric power supplied by a public utility, in a plant at Painesville, Ohio, 30 miles east of Cleveland on the shore 'of Lake Erie. The story is not without interest, since it involves several unique developments that provide the answer to a question frequently asked: How is it possible to produce magnesium metal economically at such a location as Painesville, Ohio? Basically, the answer lies in making use of facilities already in existence for the production of soda ash, which makes it possible to manufacture magnesium chloride, the principal raw material, cheaply enough to offset the high cost of electric power. To this is coupled the successful conversion of by-product chlorine into a product required for the war program. The source of magnesium for this operation is the enormous surface deposit of high-grade dolomite in the region south of Toledo, within reasonable freight haul of Painesville. This same geological stratum underlies the Painesville plant, but unfortunately at a depth of about 3000 ft. apparently too great a depth to permit underground mining to compete with the delivered cost of rock from surface quarries in other areas. The cost of dolomite obviously is an important factor, since the rock contains only some 12 per cent magnesium (20 per cent MgO) so that one dollar on the cost of stone means more than $8 in terms of its magnesium content, and more than that in terms of recoverable magnesium metal. PRODUCTION OF MAGNESIA FROM DOLOMITE In the summer of 1941, the Diamond Alkali Co. was well along with construction of a plant intended for the commercial production of refractory and other grades of magnesia from dolomite. The process to be used was designed to make maximum economic advantage of existing plant and operations by tying the production of magnesia in with the manufacture of soda ash in such a way as to make use of the lime (CaO) value of calcined dolomite. The process finally adopted after a lengthy research and development program has much in common with the old Clerc-Nihoul process, but includes certain innovations found to be necessary or

Jan 1, 1945

By Carl Zapffe

The manganese ore reserves of Lake Superior, because of their location and nature, have recently achieved a rnarked degree of importance as compared with the world's manganese reserves. To appreciate fully the significance and the adequacy of this reserve, one should understand how such ores are used, where obtainable, the quantity used, possible avenues for increasing use or application, and the chemical and physical characteristics of the available ores. Only with those data at hand, is it possible to arrive at a convincing answer to the question whether the reserves of manganiferous iron ores are adequate to satisfy the annual demand of the presently known iron ores for the full life of the latter. That they should last is vital; and to ascertain whether they will last was the purpose of the present investigation, which marks the first attempt to study these Lake Superior reserves. The Lake Superior region possesses and supplies the full assortment of iron ores needed for the conversion of ore into pig iron and steel ingots and castings. These ores are named bessemer, low-phosphorus and high-phosphorus non-bessemer, manganiferous and siliceous; and to include the term aluminiferous would be in keeping with the most recent nomenclature adopted by some dealers. About 35 or 40 years ago, perhaps less, most of the Lake Superior ore which is being used today was the material then considered either useless or too poor for immediate use; perhaps it was considered no more than a future reserve. An examination of the analyses of ores and the guarantees in the sales of those older times convince one that the opinions of those days must have been governed by only small differences in analyses. Some grades of ores used today in substantial amounts were used most sparingly only one or two decades ago. The relative quantities of the different ores used are ever changing; and, bit by bit, the metallurgy and the opinions are ever changing and the prejudices against certain ores and practices decrease. This is unquestionably more pronounced for the manganiferous ores than for any other kind. If, when using the present data for manganiferous ores, we will only be content to make allowances for the same experiences other kinds of ores

Jan 1, 1927

C. W. MERRILL*—Mr. Hughes' paper not only is very well presented but is most timely in that it covers a subject of vital interest to the United States. Tin is one of the strategic metals which has not been found here in appreciable quantities. The total United States tin output since the first recorded production over 100 years ago would not supply current consumption for a fortnight. On the consumption side, tin is extremely important in national defense because of its use in tin plate which, in the form of tin cans, makes it possible to feed properly the armies that the United States recruits from its civilian population in emergencies. Moreover, the internal combustion engines so important in powering tanks, planes, and other war machines, require large quantities of tin alloys for bearings and for soldering. These considerations, along with the fact that Malaya, historically, has been the leading source of tin to the United States, make the kind of information that Mr. Hughes has presented so ably. a matter of vital interest. Your Chairman, Mr. Romanowitz, in his introduction, referred to the fact that I had been a member of the United States delegations to the three meetings of the International Tin Study Group. Some comments on the Group's objectives and deliberations may be of interest. When it appeared that the International Tin Committee, the prewar producer's cartel, might soon revive its operations and extend its control agreement beyond the expiration date of Dec. 31, 1946, the United States Government became interested in some kind of an international trade organization concerned with tin which would give the consumers' interest equal representation with the producers' interests. An international meeting was called in London in October 1946 to consider this problem. I did not attend that meeting hut the result of the meeting was the organization of the International 'Tin Study Group which

Jan 1, 1950

By Harry K. Ihrig

THE hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1/8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was, necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes Co. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.11 The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 DESCRIPTION OF TEST METHOD The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1945

By John H. Hollomon

THE interpretation of notched-bar impact results has been a matter of controversy since the introduction of more or less standard tests by Fremont,1 Charpy2 and others at the turn of the century. Many investigators3-l1 have contributed to the understanding of the significance of such tests. Several symposiums12,13 have been held with the express purpose of discussing the significance and interpretation of the impact tests. It is not the purpose of this paper to review all these contributions to the development of the knowledge on this subject, but rather to present an interpretation of notched-bar impact tests that appears to be in agreement with the available published data. Fundamentally, the interpretation discussed in this DaDer of the brittle failure of some steels in notched-bar impact test is similar to the qualitative analysis presented by Ludwik3 in the 1920's. Essentially, Ludwik stated that the function of the notch was to increase the tensile stress necessary for yielding, and that brittle failure occurred when the stress necessary for yielding exceeded the normal stress required for fracture (with no plastic de- formation). Ludwik, however, had no means of measuring this normal stress necessary for failure of a plastically* undeformed metal, therefore he could not extend his interpretation beyond the qualitative stage. Kuntze14 and recently MC- Adam15 attempted to determine the effect of deformation on the stress necessary for fracture by testing, in tension, specimens notched to various depths and angles. Because of the uncertainties in Kuntze's (and RlcAdam's) analysis of the stresses (which have been pointed out by SachsI6) and the inherent nonuniformity in the stress distribution in notched bars, the results of such investigations are difficult to interpret. A more direct method of measuring the effect of deformation on the fracture stress was suggested in previous papers17-l8 and has been utilized in the present investigation. The present paper concerns itself primarily with the behavior of notched impact specimens. The effects of strain rate, temperature, and stress distribution, which are discussed with reference to the impact specimen, apply just as well to the behavior of metal at the bases of notches in any engineering structure. All that is necessary is to determine the stress distribution in the structure at the base of the notches.

Jan 1, 1944

By Henry M. Howe

THE natural effect of large size should be to increase segrega¬tion. I have previously pointed' to the excessive segregation in many large ingots as tending to confirm this, but I have shown that in case of ingots less than 16 in. square this expected effect of ingot-size is liable to masked by that of other variables. Under these conditions we should expect that if large ingot-size really does tend to increase segregation, this effect would be shown by taking the average of large numbers of cases, so that the effects of these other variables might off-set and cancel each other.

Jan 10, 1909

By R. F. Janke, J. F. Bossler

Introduction The commercial use of ion exchange resins to recover uranium evolved in the decade following 1950 when significant efforts were made to recover this vital element economically and efficiently from low grade ores. It was discovered that in both acid and alkaline systems, uranium exists as an anionic complex. This led to the application of anion exchange resins to concentrate and purify the uranium product. While this is the simplest statement of what an ion exchange resin does in the recovery of uranium, it should not be forgotten that the industry is continuing to evolve new methods in mining and processing which affect ion exchange operation. The inception of solution mining, the use of expanded bed ion exchange columns and the development of continuous ion exchange systems represent several examples of this continuing evolution in the industry. Throughout all of the changes in equipment designs and variations in solution compositions, the purpose of the ion exchange resin remains the same - to concentrate and purify uranium. Ion Exchange Resins When evaluating ion exchange resins for a uranium recovery project, the task that faces the chemist or process metallurgist is an assessment of the efficiency and, therefore, the economics of the various candidate resins for a given project. This assessment should include consideration of both physical factors such as particle size, density, hydraulic expansion and pressure drop as well as chemical factors such as the uranium loading and elution characteristics. For any given application, the differences in the physical and chemical behavior of ion exchange resins are a function of the conditions used to manufacture those resins. Therefore, an understanding of the way in which manufacturing variables affect resin behavior is important. Since most uranium recovery projects are concerned with recovery of the anionic complexes of uranium using anion exchange resins, this discussion will be restricted solely to the family of anion resins. The majority of the ion exchange resins used in commercial recovery operations look similar to the resins shown in Figure #1. [ ] Most of these materials are based on a styrene- divinylbenzene copolymer. The liquid monomers, styrene and divinylbenzene, are charged to a co-polymer reactor containing water. The water insoluble monomers are then mixed with the water to suspend oil-like droplets of the monomer mixture in. the water. The entire reaction mixture is then heated causing the monomers to polymerize into sol id thermoset plastic spheres. The spherical nature of the particle, the particle size distribution and the primary crosslinking level are fixed in this step in the production process. Figure 2 is a simplified illustration of this step of the process. [ ]

Jan 1, 1979

By R. S. Shoemaker, F. W. McQuiston

RECOVERY METHODS AS RELATED TO PROPERTIES OF SILVER ORES The earliest metallurgical process for treating silver ores was amalgamation with mercury which was in use in the early 1500's. Closely following was the development of the Patio process for treating ores at Pachuca, Mexico. Silver often occurs as the native metal and in deposits associated with other metals such as gold, copper, lead and zinc. Principal silver minerals include compounds of sulfur, antimony, arsenic, and copper. Silver chloride, and argentiferous galena are also prime sources. Native silver and the chloride characterize the oxide zone of most deposits. Native silver can be concentrated, amalgamated, or cyanided. Silver chloride rapidly dissolves in cyanide without oxygen. Oxidized silver ores containing the higher oxides of manganese are generally refractory to metallurgical treatment. A refractory compound of manganese and silver is formed, probably a manganite , which is insoluble in cyanide solutions. Argentite is the predominant silver mineral. Other important economic minerals are native silver, argentiferous galena, cerargyrite, pyrargyrite and tetrahedrite. Argentite dissolves slowly, the reaction being reversible requires an excess of cyanide. Argentite with disseminated fine grained gold occurring in quartz veins with minor amounts of chalcopyrite and galena may be cyanided directly after grinding, with high silver and gold recoveries. The flowsheet adapted to this type of ore is the Minas de San Luis, Tayoltita cyanide plant, which treats a high grade argentite silver ore containing gold. It is a standard cyanidation circuit but employs long periods of agitation contact for the high silver sulfide content ore. Lead-zinc base metal semi-oxidized- complex ores in pipes and chimneys are replacement deposits in limestone at El Mochito Mine, Honduras. Mineralization comprises galena, cerussite, anglesite, sphalerite, calamine, and smithsonite. The silver content of about 16 ounces occurs as native silver globs, wire and the mineral argentite. After flotation of lead and zinc concentrates, the tailings are cyanided for gold and silver recovery. The great Huelva pyritic copper deposits of Spain carry a little gold and silver. At Cerro Colorado, these metals were concentrated above the chalcocite zone into the so-labeled Mgossanu. This material with a content of 0.08-0.09 oz Au and 1.50 oz Ag per ton is amenable to cyanidation. See Cerro Colorado flowsheet. In southern Hidalgo, about 60 miles north of Mexico City, are the great silver--gold veins of one of the foremost silver mining districts of the world. Real del Monte, Pachuca. The mineralized area consists of flow rocks and intrusives. The oxidized ores carry pyrites with oxides of iron and manganese and other minerals, silver and gold. The first zone contains

Jan 1, 1975

By Frederick N. Rhines

Because of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding their occurrellce, even though the fundamental mechanisms invalved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by Processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpiet the next. It is the purpose of the present Paper to present, by means of examples drawn from practice, a brief survey of the ways in which gas-metal diffusion serves and obstructs the Purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with ' but brief mention of parallel cases. The Nature of Gas-metal Diffusion The term ugas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of " substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain.temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. NO element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By Frederick N. Rhines

Because of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding their occurrellce, even though the fundamental mechanisms invalved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by Processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpiet the next. It is the purpose of the present Paper to present, by means of examples drawn from practice, a brief survey of the ways in which gas-metal diffusion serves and obstructs the Purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with ' but brief mention of parallel cases. The Nature of Gas-metal Diffusion The term ugas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of " substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain.temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. NO element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By J. W. Marx, R. H. Langenheim

The injection of heat-bearing fluids may offer a wider application to secondary and tertiary recovery from conventional oil reservoirs than inderground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. In all cares, conduction heat losses to overburden and un-derburden will impose an economic limit upon the size of the area which can be swept out from any one injection point for any given set of conditions. The present report describes a method for c.rtin~ating thermal invasion rates, cumulative heated area, and theoretical economic limits for sustained hot-fluid injection at a constant rate into an idealized reservoir. Full allow-ance is made for non-productive reservoir heat losses. Required solutions can be obtained directly from the numerical tables given here, as soon as all operating conditions are specified, withou extensive mathematica1 ~nanipulation on the part of the user. The injection of a heat-bearing fluid into a reservoir is frequently proposed as a means of secondary or tertiary oil production. This form of thermal recovery may offer a wider application to conventional oil reservoirs than underground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. Because of its large gross heat capacity, steam appears to be the most efficient heat injection medium, although mixtures of steam and other gases, hot water, hot oil and hot non-condensable gases also have been employed. Whatever the nature of the injection medium, economic evaluation of such thermal recovery processes will depend upon thermal invasion rates, or rates of productive reservoir heating, at any given time after the start of heat injection. In all cases, conduction heat losses to overburden and underburden will impose an economic limit upon the size of the area which can be swept out from any one injection point, for a given set of reservoir conditions, at any given heat injection rate. The present report describes a method for estimating thermal invasion rates, cumulative heated area and theoretical economic limits for sustained heat injection at a constant rate into an idealized reservoir, making full allowance for non-productive reservoir heat losses. Required solutions can be obtained directly from the nu- merical tables given here, as soon as all operating conditions are specified, without extensive mathematical manipulation. It should be noted that ordinary water flooding may be used to move an annular-heated zone outward, even though the economic areal limit for straight heat injection has been reached. Thus well spacing need not be confined to the areal limits as determined here. However, the present calculations do not cover such supplementary heat scavenging programs. The operating element consists of a radial flow system, concentric about the point of injection, with the idealized step function temperature profile illustrated by the dashed line in Fig. 1. The solid curve shown in Fig. 1 gives a qualitative picture of the true radial temperature distribution. It will be shown later that the expressions given below, which are derived from the simplifying step idealization (dashed line in Fig. I), also can be interpreted in terms of the more realistic temperature distribution shown in Fig. 2. For this case, the thermal invasion radius is simply redefined as the distance from injection well to the mid-point of the temperature distribution.

By F. R. Archibald, C. M. Nicholson

THE present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay. There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity but they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time pending review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3460,000. The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1948

By Richard E. Gray, Robert W. Bruhn

INTRODUCTION Underground coal mining has been practiced in the United States for over 200 years. Much early mining was not as efficient as today and unrecovered coal pillars, often of variable size and spacing, remain to support the overlying strata after mining has ceased. These conditions constitute a potential subsidence problem since the pillars will eventually fail. The possibility of subsidence above an abandoned mine must be anticipated except when total extraction has been achieved, permitting subsidence concurrent with mining, or when large coal pillars which have an adequate factor of safety for long-term support remain in the mine. Coal is found in 37 states and is mined under- ground in 22 states (HRB Singer, Inc. 1980). Underground mining produced 40 percent of the 7.5 x 10" kg. (830,000,000 tons) of U. S. coal mined in 1980 (Keystone, 1981). There are approximately 70,000 abandoned or inactive underground coal mines in the United States and approximately 2000 active underground coal mines (NAS/NAE, 1975). Underground coal mining in the United States will eventually extend beneath 162 x 109m2 (40 million acres). Thirty-two billion m2 (8 million acres) are already undermined (HRB Singer, 1977). Subsidence due to mining has affected more than 8 x 109m2 (2 million acres) in 30 states, 7.7 x 10 9m2 (1.9 million acres) from bituminous coal mining and the remainder primarily from anthracite mining (Johnson and Hiller, 1979). Subsidence from all other underground mines has affected only 6.9 x 10 7m2 (17,000 acres) (Johnson and Miller, 1979). Subsidence appears to be particularly widespread in two states, Pennsylvania and Illinois, although serious subsidence is found in localized areas of numerous other states (HRB- Singer, Inc. 1977). Host underground coal mining has occurred in the eastern United States, where the U. S. Bureau of Mines estimates 1.6 x 109m2 (398,600 acres) in urban areas in 18 states (out of a total 1.7 x 109m2 1418,400 acres]) are threatened by subsidence (Table 1) (Johnson and Miller, 1979). Pennsylvania and West Virginia contain 57 percent of the total threatened areas. The U.S. Bureau of Mines estimates the total cost to stabilize the estimated 1.7 x lo9m2 (418,400 acres) of subsidence prone urban land located above abandoned mines is over $12.5 billion (1978 costs).

Jan 1, 1982

By J. W. Walker, G. J. Heuer, E. W. Hough

An improved apparatus is described for the deterrni-nation of interfacial tension* by the pendant drop method in the pressure range from 15 to 15000 psi and the temperature range from 100º td 280°F. The chief characteristics of this apparatus are reliability and ease of operation. Temperature control was accomplished by means of an electrically heated jacket which could he completely removed while cleaning the apptrratus. The cell was designed so that the camera could he placed about I in, from the window without overheating the carnera lens. Separate "0" rings employed to seal each window and corresponding window backup plate gave very reliable window operation at 10,000 psi. An extra pistorr-cylinder combination was added so that a high compression ratio could he attained when gas was employed as one phase in the pendant drop cell. Other essential parts of the system were similar to an apparatus already described.' The interfacial tension for carbon dioxide and water varies from about 69 dynes/cm at 15 psi to about 19 dynes/cm at 1,250 psi for 100°F. For pressure.r between t,500 and 3,500 psi, the interfacial tension is between 32 and 24 dynes/cm at this temperature. The interfacial tension at 280°F varies from about 50 dynes/cm at 200 psi to about 17 dynes /cm at 10,000 psi. The maximum surface excess for carbon dioxide, assuming the surface excess of water to be zero, occurs at about 1,500 psi jor the 100°F isotherni and Itas a value of about -79 X 1014 mol/sq cm. At 160°F this maximum IS shifted to about 2,000 psi and has a value of about 10 X 1014 111ol/.sq cm. Other maxima, us well as several minima, are present at these and other temperatures. Judging from the data on the solubility of water in carbon dioxide at elevtrted pressures2,3, it appears that the principal maxinza natned are in regions of increasing solubility of the water in the carbon dioxide rich phase. INTRODUCTION AND APPARATUS A pendant drop interfacial tension apparatus which would accommodate an opaque liquid in a gas phase was constructed several ycars ago' for industrial purposes. This apparatus was used as a starting point for the present development. The objective of the present development was to enhance reliability and convenience of operation. Other articles'" have described pendant drop apparatus which could not accommodate a gaseous phase adjacent to the windows. A schematic diagram of the apparatus is shown in Fig. 1. The water used followed the path; A, intro-

By L. H. Wolfe, J. O. Thieme

The tensile and shear strengths of frozen soil and the compressive strengths of ice and frozen soil were measured These tests showed that the strength of ice and of frozen soil increased as the temperature was decreased. A method is presented for the measurement of thermal conductivity and specific heat of earth and ice. Using the parameters thermal conductivity, specific heat and density, the thermal diffusivity was calculated. Results of thermal property tests establish water as the major variable contributing to thermal property values. INTRODUCTION During the last few years, a considerable interest has developed in underground storage of cryogenic liquids such as liquid natural gas. Because of its economy and safety, underground storage is being used. Before underground caverns could be seriously considered, however, the strength and thermal characteristics of the soil had to be obtained. Methods are presented herein for measuring tensile, compressive and shear strengths, specific heats and thermal conductivities. The tests were performed on two soils at temperatures from ambient to -195C. Because it is difficult to find data in the literature that pertain to a particular soil, ice was used to evaluate some of the experimental procedures. Some of our ice data are compared to the published values. PHYSICAI, PROPERTIES SOIL SELECTION AND SAMPLE PREPARATIONS The physical and thermal tests were performed on recompacted samples of two typical soils that might be encountered in underground caverns: a gray, fire clay that had been pulverized and mixed with water into a pliable mud; and a brown, sandy silt that was dug from a dry river bank and subsequent1y mixed with tap water. The moisture content of the test specimens was 17 to 22 per cent (based on the wet weight of the soil). This amount of water nearly saturated the silt, but the clay was well below the saturation point. The soils are partially described by the sieve analyses (Fig. 1) which show the particle size distribution of the coarser than 44 micron portion of the soils. The curves also show that approximately 75 per cent of the clay and 20 per cent of the silt are finer than 44 microns. The particle size seems to affect some of the physical properties, and the finer than 44 micron portion is important in the thermal conductivity test. Physical specimens were cut with a bandsaw from frozen blocks of the soil. The specimens were then sanded and kept frozen until after they were tested. They were stored at the approximate test temperature for several hours. Then, to equilibrate the samples to the test temperature, they were stored at the temperature at least an hour before they were tested. TEST EQUIPMENT An Instron, which is a constant speed gear-driven instrument, applied force to the samples and drew stress-strain plots of the test. All of the samples were strained at 0.02 in./min. All of the physical tests were conducted in a temperature cabinet that controlled the temperature to 1C. TENSILE STRENGTH Briquette or "dog-bone" shaped tensile specimens were pulled with suitably shaped jaws. This shape of specimen, which is usually used for tensile tests of concrete, is satisfactory for testing frozen soils except that the samples tend to

Jan 1, 1965

DEPENDENCY on foreign sources for many mineral raw materials is a characteristic of our economy which is becoming painfully evident. Although investment in foreign mining projects has increased, it has not kept up with the growing demand for foreign minerals. The sphere of American investment capital in mining ventures abroad has been severely limited by the rise of nationalism in many underdeveloped countries. Consequently, we can look back over half a century in which mining investment, exclusive of petroleum, has increased by 50 pct whereas other American investments abroad have multiplied by better than 300 pct. Investment in foreign mining or petroleum encounters different problems than capital investment for other industries. It is rarely invested in industrialized nations. Most of it goes to countries with expanding frontiers, like Canada, or to underdeveloped nations like Liberia. It must be used for building communities, recruiting and training labor, and establishing lines of communication and transportation. These complications are an accepted part of the mining game. However, the most complex problem is in those countries which consider mineral exploitation a usurpation of the people's natural heritage. This is a characteristic of the young government existing by a tenuous balance of power in an underdeveloped nation. American mining capital understandably has shunned these nations as being poor investment risks. However, they possess minerals which are needed by industry. Our government has attempted to stimulate mineral supplies beyond those provided from abroad by private capital. ECA, now under DMPA, makes loans to foreign mining companies. Since the ECA program cannot be expected to continue indefinitely, Point IV seems to be the logical next step to encourage foreign countries to fill our shortages. However, only 1 pct of the $35 million budget provided in the first year for Point IV was alloted for mining programs. Considering the need for minerals and the difficulties of procuring them by private investment, a larger share is needed and justifiable. Those who have been engaged in foreign mining can vouch for the fact that it takes many decades to teach the complex technology and economics of mining to the natives of under-developed countries. For this reason Point IV must be considered a long range program. Mineral requirements for the present must be met by more direct measures. Encouragement of private investment in foreign mining by such incentives as tax relief on profits from foreign sources, international bank-borrowing facilities for private capital, and diplomatic assistance in encouraging foreign countries to cooperate are imperative for our future mineral security.

Jan 1, 1952

By Harvey S. Mudd

AMONG the highly skilled craftsmen of the Renaissance were those who worked with ores and metals. The author of this book, Vannoccio Biringuccio, was a master craftsman in the practices of smelting and of metalworking. Contrary to the customs of a trade, Biringuccio was moved to impart his knowledge to all and thus he has given us the earliest hand- book on metallurgy-in fact, the first printed book dealing with the applied metal arts and the processes of ore reduction. We should remind ourselves that metallurgy is an ancient art and then it fair1y may be said that Biringuccio sought to describe the techniques that had been in course of development since the Bronze Age of western civilization. Whether Biringuccio was a man of learning or a scholar according to the standards of his time we do not know, but today we recognize him as a man of science who gave his wisdom to succeeding generations. It was not until the coming of the Power Age at the end of the eighteenth century that progress was resumed in the science of which he wrote more than two hundred years before. Little is known of Biringuccio's training in his native Siena. It can be surmised that there, as in Florence, where his contemporary Benvenuto Cellini lived, he received his training in the craftsman shops where the industrial arts were taught and flourished alongside the fine arts. Perhaps he and Cellini were acquainted, although there is no mention of Biringuccio in Cellini's autobiography-an omission that Cellini's vast egotism makes understandable. He was the great artist, and Biringuccio was a practical, studious, unromantic figure with no favors to dispense. In the April 1940 issue of Mining and Metallurgy Dr. Smith describes Biringuccio's book under the title of "A Neglected Italian Metallurgical Classic." The article, revised and extended, forms the basis of the introduction to the present volume, and I urge all who take up Pirotechnia to read what Dr. Smith has written in the Introduction. Biringuccio's work is a classic and in its translation Dr. Smith and Dr. Gnudi have brought to bear the high degree of scholarship that it deserves. Dr. Gnudi made the translation at Dr. Smith's request and it was then refined "in the fire" of his scientific knowledge of the subject. The result is a book which the Institute is proud to place before its members and which the Memorial Fund Committee considers it a privilege to publish.

Jan 1, 1942

By William Kent

(Read at the Amenia Meeting, October, 1877.) IN a paper by Mr. Frank Firmstone, published in vol. iv, of the Transactions of the Institute, on "Comparison of Results from Open-topped and Closed-topped Furnaces," the regularity of the average grade of pig iron produced by the furnace under different conditions is expressed by means of a curve or diagram. The object of this note is to show that the graphic method, or that of representing variations by plotted curves or diagrams, is capable of a much more extended application to blast-furnace records, making a valuable auxiliary to the "furnace .book," and that by it the practical metallurgist may obtain at a glance information concerning the variations of the furnace during long periods, which could be found in the furnace book only after a tedious search. Plate XII is a graphic record of an anthracite blast furnace for one month. The table on page 554 gives the figures obtained from the furnace book, together with a record of temperature of the atmosphere, barometric pressure, and moisture in the air, which was obtained from a meteorological observatory not far from the furnace. In the records of a furnace, two of the variable qualities are final results, viz., the quantity of pig iron produced, and its grade; all the other variables are antecedent causes which produce the final results. Of these variable causes which contribute to the quantity of product and its grade, some are partially under the control of the furnace manager, others depend upon the state of the atmosphere, and still others are accidental. Of the first class are the character of the materials charged, and their relative proportions, their mechanical conditions, as wet or dry, large or small pieces, etc., the revolutions of the engine, the heat and pressure of blast, and the distribution of the charge. Of the second class are the number of pounds of air blown into the furnace for each stroke of the engine, the amount of moisture in the air, and the condition of the chimney draughts. These vary largely with the season of the year. Of the third. class is the leaking of a tuyere or a temporary stoppage. To keep a record of this kind for a whole year, it is only necessary to procure a sheet of common profile or cross section paper, about 38 inches long and 8 or 10 inches wide, with cross lines ruled about 0.1 of an inch apart. The vertical lines, or those in direction of the

Jan 1, 1878

By W. J. Sharwood

Cupellation is well known to be one of the most effective methods of separating silver and gold from base metals and other impurities, as well as one of the most accurate means for their estimation. In the latter application it consists in absorbing in some porous medium the fused lead oxide formed by the oxidation of the lead "bath," which carries with it the oxides of other base metals present. It has long been recognized that small amounts of both silver and gold were removed and absorbed together with the base metals, as well as being to some slight extent volatilized, and in work of the highest accuracy a correction is made for the "cupellation loss." Thus in the assay of bullion this is done by means of "proofs" of like composition, which are manipulated throughout in precisely the same manner as the assay pieces, and are assumed to lose or gain like amounts. In the case of certain very rich ores and commercial products the loss is adjusted by assaying the cupel itself and recovering the precious metal absorbed, but this doubles the labor and does not remedy the loss by volatilization. Arbitrary tables have been drawn up by various authorities with the object of enabling a correction to be applied without the use of a check. These have been of very limited practical use owing to the fact that a number of factors affect the losses sustained. For a fixed amount of precious metal the loss varies with the amount of lead used, with the nature and amount of the impurities, with the porosity of the cupel, with the air supply, and above all with the temperature at which cupellation is carried on. Pure silver loses relatively much more than gold, but the loss in either is diminished by an addition of the other metal. The concentration of precious metal in the litharge increases as the concentration in the lead increases, but little work has been published connccting the two. If all other conditions remain the same the actual total loss increases, but the percentage loss diminishes, with an increase in the weight of precious metal treated. The results of an immense number of experiments have been published at various times- during the past hundred years giving the actual or the percentage losses suffered under various conditions of cupellation, but the data are widely scattered and few attempts have been made to correlate them, so that no definite law has heretofore been shown to exist

Jan 1, 1916