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By Haydn H. Murray, Sam H. Patterson

The term clay is somewhat ambiguous unless specifically defined, because it is used in three ways: (1) as a diverse group of fine-grained minerals, (2) as a rock term, and (3) as a particle-size term. Actually, most persons using the term clay realize that it has several meanings, and in most instances they define it. As a rock term, clay is difficult to define because of the wide variety of materials that compose it; therefore, the definition must be general. Clay is a natural earthy, fine-grained material composed largely of a group of crystalline minerals known as the clay minerals. These minerals are hydrous silicates composed mainly of silica, alumina, and water. Several of these minerals also contain appreciable quantities of iron, alkalies, and alkaline earths. Many definitions state that a clay is plastic when wet. Most clay materials do have this property, but some clays are not plastic; for example, halloysite and flint clay. As a particle-size term, clay is used for the category that includes the smallest particles. The maximum-size particles in the clay-size grade are defined differently on various grade scales. Soil investigators and mineralogists generally use 2 micrometers as the maximum size, whereas the widely used scale by Wentworth (1922) defines clay as material finer than approximately 4 micrometers. Some authorities find it convenient to use the term clay for any fine-grained, natural, earthy, argillaceous material (Grim, 1968). When used this way, the term includes clay, shale, or argillite, and some argillaceous soils. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, the term is generally understood by those who use it. Clay is an abundant natural raw material, and it has an amazing variety of uses and properties which will be discussed in this chapter. Clays rank among the leading industrial minerals in both tonnages produced and total value. Their importance is indicated in Table 1, which lists the 1978, 1979, and 1980 production and values according to the US Bureau of Mines (Ampian, 1980). Statistical data summarizing world production of kaolin, bentonite, and fuller's earth are compiled by the US Bureau of Mines (Ampian and Polk, 1981). The total world bentonite production in 1980 was 6,625,204 st of which the United States produced 4,184,619 st. The total fuller's earth produced in the world in 1980 was 1,952,600 st of which 1,534,000 st was produced in the United States. The total world kaolin production in 1980 was estimated at 22,971,000 st. Approximately 13 million tons of this total was produced in two countries, the United States and the United Kingdom. World production data on ball clay, fire clay, and miscellaneous clays are not available. As industrial minerals, clays are a complex group that consists of several mineral commodities, each having somewhat different mineralogy, geologic occurrence, technology, and uses. In this chapter these commodities are organized as follows: (1) bentonite and fuller's earth; (2) kaolin, ball clay, halloysite, and refractory clays; and (3) miscellaneous clay and shale. Bentonite and fuller's earth are grouped together because they are closely interrelated. Though bentonite is a term based on mineral composition and fuller's earth is a term based on use, the two are virtually inseparable, because much, but by no means all, clay sold as

Jan 1, 1983

By James Gayley

The atmosphere, which plays such an important part in the manufacture of iron and steel, is the most variable element involved in its several processes; and particularly is this true of the blast-furnace process, which consumes air in large quantitiee. At no time since the blast-furnace became an important and widely used apparatus—even when it was operated in the most crude manner—have the variations in composition of the raw materials used been as frequent and as great as the variations in humidity of the atmosphere. Important improvements have been made in the blast-furnace and its accessories, such as the hot-blast stoves, the increase in size and change in the shape of the furnace, more efficient blowing-engines, the increased protection given to the bosh-walls, and the careful preparation of the raw material, all of which have exerted a pronounced influence on the furnace-operations from a metallurgical standpoint. But during the past eight years little advance has been made in this direction; the fuel-consumption has not diminished, nor has there been any material increase in production. Within that period, however, there has been witnessed the greatest development in appliances for the economical handling of material. So complete has been the work in this direction, that, except in isolated cases, in this country at least, a further extension does not hold out much promise of a satisfactory return on the investment required. It seemed that, with the exception of the gas-engine, we had about reached the limit, for like a strong wall, the atmosphere, with its humidity as variable to-day as when first blown into a primitive blast-furnace, appeared to stand as a barrier to

Jan 1, 1905

By W. L. Staker

The Bureau of Mines investigated selective extraction of Au and Ag from a low-grade Au ore containing Hg. Gold and silver were extracted from the ore in cyanide slurries, and Hg extraction was suppressed with sodium or calcium sulfide. Maximum Au extraction and minimum Hg extraction were obtained using solutions containing 0.34 lb NaCN/ton of solution. Increasing the cyanide concentration increased Hg extraction without increasing Au extraction. Mercury extraction from the ore was suppressed with 0.5 to 2.9 lb CaS/lb Hg in the ore. Gold-to-mercury ratios of 100:l to 400:l were obtained in the leach solution, and on the activated carbon in a CIP circuit.

Jan 1, 1984

By Joseph T. Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned. Previous Theories of Origin Descriptions of the deposits and theories of their origin have been concerned mainly with Iron Mountain and Pilot Knob, which represent the two contrasting types of occurrence. The Iron Mountain deposits have been considered of close magmatic origin by Whitney' in 18.54, Geijer2 in 1915, and Spurr3 in 1927. Whitney referred to them as of eruptive origin. Geijer considered them fissure fillings at magmatic temperatures. Spurr called them vein dikes formed from ore magma which was essentially fluid iron oxide. Schmidt4 in 1872 ascribed them to fissure filling by thermal chalybeate waters of meteoric origin. Nason5 in 1892 advanced essentially the same explanation. One of the best

Jan 1, 1929

By N. H. Darton

In the coastal plain region of the middle Atlantic slope there are no large supplies of potable surface-waters. The great rivers by which the region is intersected are tidal estuaries, and the water of their local branches is often of bad quality. The cities situated at intervals along the western margin of the region obtain a plentiful supply of excellent water from the rivers above the tidal estuaries, but out on the coastal plain surface-waters are mainly used. A few artesian wells have been sunk which afford abundant water, but their number is at present very limited. Norfolk, Newport News, and the many smaller places use surface-waters, and all over the region there is great need for purer and more abundant supplies. During the past five years I have been engaged in a study of the geology of the coastal plain for the U. S. Geological Survey, and have given special attention to the question of subterranean waters. In this communication I shall present a brief review of the geological conditions under which such waters occur in this region, and give an account of the wells which have been bored. Unfortunately the number of well-records is small, and some of the most important questions of subterranean geology are as yet far from settled. It is hoped that this paper may lead to further borings, especially as the cost of artesian wells has been much reduced by the introduction of new machinery and methods, and is now quite within the reach of the average community. In New Jersey there are many wells, and the water-bearing horizons are so definitely determined that they may almost everywhere be predicted with certainty. In Maryland and Virginia the data are less definite, but there is excellent evidence of a wide distribution of water at moderate depths.

Jan 1, 1895

By R. M. Brick

THE etched microstructures of cold-worked alpha brasses, after reduc-tions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonomously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {111}, in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson5 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into sym-metry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

Contents A - Metal Mining B - Minerals Beneficiation F - Coal H - Industrial Minerals I - Mining Geology L - Geophysics

Jan 11, 1953

By G. S. Brooks

WITH the gradual depletion of the natural-gas pools of the Kansas district, together with the uncertainty of further cheap fuel developments, some. of the western zinc companies turned to the coal fields, attracted by their permanency and the 'success of the Matthiessen & Hegeler Co. and the Illinois Zinc Co. Being then confronted with the problem of using a relatively high-priced fuel, although the ultimate' supply was very great, the fuel economies of the kilns and furnaces became of far more importance, and the more modern equipments, as a result, embodied distinct gads in this phase of the business. In addition, there have been some pronounced advances in the actual making of gas from these coals. Increased efficiency in gas making has contributed its share to lowering costs and those plants located in the higher priced fuel districts have probably been obliged to study these economies somewhat more closely. Naturally, many beneficial changes have resulted in both practice and apparatus in these sections. On, certain western coals, for instance, the actual saving in fuel consumption has been 50 per cent. By this is meant that, where about 1.75 tons were burned to smelt 1 ton of oxidized ore, 0.7 to 0.9 ton is now required. While comparisons by W. R. Ingalls1 of fuel economies in smelting in this country and Germany before the war may, in general, be correct, they do not appear to-do justice to the more progressive. American practice. It is doubtful whether German plants were substantially bettering these fuel ratios. Data furnished by Bender and Frams do not afford records averaging less than 0.9 ton coal per ton ore on materials from 40 per cent. to 50 per cent. zinc.

Jan 9, 1919

By Alexander Field

The hot-rolling properties of a series of high-sulfur steels are described. From a consideration of the sulfur, manganese, and zirconium contents of these steels, it is shown that zirconium reacts with the sulfur content of molten steel in accordance with the equation Zr + 2S = ZrS2. Zirconium disulfide appears in the finished state as gray-colored inclusions, similar to manganese sulfide in plastic behavior and general appearance. Zirconium completes its act of deoxidation before proceeding to combine with sulfur and indirectly increases the effective sulfur-combining power of any manganese which may be present. IN A previous paper,1 the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of "red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the reaction between zirconium and sulfur in molten steel may he represented by the simple equation, Zr + 2S = ZrS2, and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion.

Jan 2, 1924

By Munroe F. Warner

As originally built, the plant of the American Zinc and Chemical Co. at Langeloth, Pennsylvania, was based upon the Joplin and Wisconsin fields as primary sources of zinc ores, the ores being the then normal jig and table concentrates. Construction incorporated standard Matthies-sen and Hegeler kilns without regenerators. With the development of differential flotation, zinc concentrates produced by that process became the basis of operation. These concentrates were very fine, upwards of 90 per cent passing a 300-mesh screen, and had a comparatively low fusing point with marked caking and crusting characteristics. Difficulties and losses quickly developed. In roasting, the ore went through a decidedly fluid state, and spills became serious. Caking and crusting on hearths was severe and dust losses throughout became intolerable. Acid recoveries dropped from the normal ton-for-ton level to 0.85 tons per ton of ore, and choking of Glover towers and acid lines became a problem. In 1926 and 1927 a two-unit sintering plant was built and placed in operation in accordance with the Baelen process for finishing desulphuri-zation with admixture of carbon. This had its beneficial effect in smelting, but the other problems remained. The problem presented was the roasting of Pecos flotation concentrates at the rate of 200 tons daily to a sulphur content suitable for finishing in the sintering plant. Specifications had to be governed by the existing acid plant of four chamber sets built in units of two, rather widely separated, and the sintering plant built in the space between the existing pairs of kilns, of which there was one on the center line of each of the four chamber sets. The problem contained elements of pioneering and experimentation. A thermal analysis and heat balance clearly demonstrated a possibility of accomplishing autogenous roasting, well worth the attempt, because of high fuel costs and resultant economies in operation of the acid plant due to decreased gas volumes and a consequent release of capacity for increasing acid production, a problem also faced.

Jan 1, 1937

By L. M. Pidgeon

The reactive metals are above manganese on the electromotive series. Their compounds are characterized by large heats of formation and they cannot be reduced from their ores by classical methods. Three general production methods have been used: a) Fused salt electrolysis, b) reduction of a halide by another metal, and c) reduction of the oxide by another metal. Method (a) is highly developed, as in the case of aluminum, (b) in the case of titanium, and (c) has been successful in the case of volatile metals such as magnesium and calcium. It is suggested that future improvements will take place in (a), and particularly in (c), but are rather less likely in the case of (b). THIS year of 1963 is the centennial of the birth of both Charles Hall and of Heroult, the founders of the aluminum industry. Aluminum is the one reactive metal which has reached massive stature in modern industry and perhaps the only such metal to have been produced in any quantity before the turn of the century. It has been joined by others, some on a very modest scale, but all of importance and all of fascinating interest. When invited to give the Fifth Extractive Metallurgy lecture, it seemed appropriate to look back upon the short history of this group to trace the developments which brought extraction methods to their present state and, at great risk, offer opinions as to future trends.

Jan 1, 1963

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,' and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Wheeler P. Davey, Robert T. Phelps

A study of solid solutions has long been a source of interest because of the conditions controlling their formation. X-ray investigations so far have been conducted with the idea that there were two types of solid solutions. In the first type, an atom of the solute was supposed to replace an atom of the solvent in the crystal lattice. In the second type, an atom of the solute was supposed to lie in one of the interstices between the atoms of the solvent. These pictures both require that the sizes of the atoms must play an important part in the process of solution. It is the purpose of the present investigation to study the mechanism of solid solution, using pure silver as the solvent, and pure aluminum as the solute. X-ray measurements show that these elements have the same "shape" of atomic domains1 (they both crystallize as face-centered cubes) and that their atomic diameters differ by less than one per cent.' The results of the present investigation point toward a chemical rather than a physical picture of the nature of solid solution, and make the older pictures merely special cases of a more general picture. The new theory has the advantage, too, that it offers a rational explanation of certain phenomena which hitherto have been only interesting detached facts. The aluminum-silver system which was chosen for this study has been studied by various methods by several workers. By means of thermal analysis Gautier2 and Petrenko3 have determined the phase diagram. Hansen studied the aluminum-rich alloys by means of thermal and microscopic analyses. He showed that at high temperatures silver dissolved in aluminum to the extent of 47 per cent by weight at 560" C. But this solubility decreased to 1 per cent at 200" C. Westgren and Bradley5 made an extensive X-ray study of these alloys. They used the change in the lattice parameter of silver as a criterion of the solution State College, Pa.

Jan 1, 1932

By Reynold Q. Shotts

The small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive ac-in of coke in the form of ''trees,, or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of labora- tories1,2,3,4,5 are one method of approach to the problem Of selecting stoker coals- As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that Others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simp1e measure Of the tendency Of a a to form coke in a fuel bed. Although possessing all Of the disadvantages Of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects Of swelling properties upon combustion.7 Ostborg, Limbacherand Sherman, have shown that the test can Predict, roughly, the tendency Of coke to accumulate in the fuel bed Of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1949

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By Steve H. Carpenter, Henry E. Otto

The explosive welding of metals is dependent upon the production of a jetting action caused by the collapsing of one metal plate against another. Successful welds are generally accomplished if the yield strength of the metals is in the range of 10,000 to 90,000 psi and the sonic velocity of the metal is greater than the detonation velocity of the explosive if direct contact explosive is being used.' Should the detonation velocity exceed the velocity of sound in the metal it may still be possible to obtain the jetting action and a good weld. However, in most cases where a high detonation velocity is used complications arise because of reflected shock waves which tear the bond apart as fast as it is put together.' Explosive welding of lead presents several problems since its yield strength and sound velocity are very low. Various values have been published3-5 for the velocity of sound in lead ranging from 2000~ to 23004 m per sec. Most of the high-order explosives have detonation velocities on the order of 6000 to 8000 m per sec, which precludes their use. The dynamites have a lower detonation velocity of around 2800 m per sec which is still somewhat too high. Lower-order explosives such as ammonium nitrate (1070 m per sec) must be used to weld lead in the as-received condition if the explosives are used in direct contact. Rather than use low-order explo'sives it was decided to alter the sonic velocity of the lead. The sonic velocity is directly related to the modulus of the material according to the following expression: Fig 1—Interface of explosive weld of lead to steel. Lead is on top As-polished Magnification 75 times as well as the yield strength. Bolling et al. 6 show that the shear modulus of lead single crystals increases from about 0.72 X1011 dynes per sq cm at 300°K to about 0.98 X1011 dynes per sq cm at 0°K, an increase of approximately 3 5 pct. This gives an increase in the sonic velocity of around 700 m per sec. Hence, the sonic velocity of lead at cryogenic temperatures is approximately equivalent to the detonation velocity of the low-order dynamites. We have obtained high-quality lead to steel explosive welds using a 40 pct dynamite in direct contact with the lead. Prior to detonation the lead was chilled with liquid nitrogen (78°K) to increase the strength and sonic velocity. Welds were made while the lead was cold. Specimen sizes were 3 by 6 in. A preset angle of 5 deg with a 0.10-in. standoff at the base was the geometrical setup used. The amount of explosive used for optimum welding of an 1/8 -in. -thick lead sheet to a steel plate was found to be 7 g per sq in. A PETN sheet explosive line wave generator was used to insure a linear detonation front through the dynamite. A photomicrograph of a lead-steel weld is shown in Fig. 1. The typical wave effect that constitutes a good explosive weld is present. When tested in shear, the weld failed in the lead, indicating that the bond is stronger than the lead base metal. Higher-order explosives were also tried without success. We believe this indicates the importance of matching the detonation velocity and the sonic velocity for successful explosive welding. Note Added in Proof. High quality explosive welds of lead to steel have recently been obtained at ambient temperature using a low velocity (1000 M per sec) free running dynamite. The weld interface obtained is comparable to Fig. 1. 'S. H. Carpenter, R. H. Wittman, and R. J. Carlson: Proceedings of the First International Conference of the Center for High Energy Forming, Syracuse University Press, syracu.se, N. Y., in press. 'A. HI Holtzman and G. R. Cowan: Welding Risearch. Council Bull., No. 104, April, 1965. 'Metals Handbook, 8 ed., p. 1062, Metals Park, Ohlo. 'J. M. Walsh, M. H. Rice, R. G. McQueen, and F. L. Yarger: Phys. Rev., 1957, vol. 108, pp. 196-216; 'L. V. Al'tshuler, K. K. Krupnikov, B. N. Ledener, V. I. Zuchikhin,

Jan 1, 1968

By L. C. Graton

The federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal industries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Because of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final and may conceivably be very materially increased. For 1918, the taxes are expected to be still greater, but no compilations are yet available. Taxes at a high rate are to continue indefinitely. The subject is clearly of gravest import to the mining industry in particular. The Commissioner of Internal Revenue, who is charged by law with the administration and collection of the taxes, is determined that these functions shall be performed in a just and businesslike way. Fairness and finality are to be the chief objectives. In view of the peculiar conditions that attach to the tax program as applied to mines and other wasting industries, like oil, gas, and timber, the Commissioner has resorted to professional advice and assistance by manning a Sub-division of Natural Resources with competent engineers, brought in from the several industries, into whose hands he has placed for solution the technical questions involved. These engineers have a two-fold duty: (1) to devote to the solution of these problems their own knowledge and experience; (2) through their acquaintance with their respective industries, and with the men engaged in those industries, to focus upon these problems, by conferences and otherwise, the best opinion of the country. The principal object of this paper is to acquaint the mining profession with the attitude of the

Jan 1, 1923

By L. C. Graton

The federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal industries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Because of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final and may conceivably be very materially increased. For 1918, the taxes are expected to be still greater, but no compilations are yet available. Taxes at a high rate are to continue indefinitely. The subject is clearly of gravest import to the mining industry in particular. The Commissioner of Internal Revenue, who is charged by law with the administration and collection of the taxes, is determined that these functions shall be performed in a just and businesslike way. Fairness and finality are to be the chief objectives. In view of the peculiar conditions that attach to the tax program as applied to mines and other wasting industries, like oil, gas, and timber, the Commissioner has resorted to professional advice and assistance by manning a Sub-division of Natural Resources with competent engineers, brought in from the several industries, into whose hands he has placed for solution the technical questions involved. These engineers have a two-fold duty: (1) to devote to the solution of these problems their own knowledge and experience; (2) through their acquaintance with their respective industries, and with the men engaged in those industries, to focus upon these problems, by conferences and otherwise, the best opinion of the country. The principal object of this paper is to acquaint the mining profession with the attitude of the

Jan 1, 1923