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By G. R. Speich

A cellular precipitation reaction in which cells consisting of an Ni3Ti (DO24) phase and austenite are formed has been studied in an austenitic Fe-30 Ni-6 Ti alloy. The variation of the growth rate and interlamellar spacing of the Ni3Ti cells with temperature has been determined m the range 400" to 975°C; the interlamellar spacing is proportional to the degree of undercooling; the growth rate can be expressed by an equation of the form G = K?T)2 exp(-Q/RT). The habit of the Ni3Ti lamellae is (001)Ni3Ti (111)y;[010]Ni3T2 [010]y. An almost perfectly coherent interface is formed between Ni3Ti lamellae with this orientation rela -tionship and the intervening austenite. This first Ni3Ti cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. CELLULAR precipitation reactions have been studied in copper-base,1,2 Au-Ni,3 pb-sn,4 and iron-base ferritic5,6 solid solutions, and this mode of precipitation has been treated theoretically by smith," Turnbull,8,9 cahn,10 and more recently by bohm.11 In the case of substitutional austenitic iron-base alloys little or no data are available, Cellular precipitation reactions are well known in austenitic nickel-base alloys12,13 but usually these reactions do not proceed to completion because of general precipitation occurring in the matrix, and they have not been studied in detail. Precipitation from an austenitic Fe-30 Ni-6 Ti alloy was studied as part of a larger investigation of the mechanisms of precipitation from substitutional iron-base alloys. This alloy, austenitic at high temperatures, decomposes at lower temperatures by a double cellular precipitation reaction. The first decomposition product consists of alternate lamellae of an Ni3Ti(DO24) phase and austenite. The reaction proceeds to completion, consuming all of the original austenite. This first cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. The first cellular reaction was studied in detail by light and electron microscopy, hardness measurements, and by X-ray and electron diffraction. Interlamellar spacings and growth rates were measured during isothermal aging in the range 400" to 975°C. The orientation relationship between the Ni3Ti and austenite lamellae was determined and indicates that an almost perfectly coherent interface exists between the two phases. This first Ni3Ti cellular reaction is of particular interest because it occurs over such a wide temperature interval. This allows cellular growth rates and interlamellar spacing data to be obtained for much larger degrees of undercooling than reported hitherto. MATERIALS AND EXPERIMENTAL PROCEDURE The Fe-30 Ni-6 Ti alloy was prepared from electrolytic iron, Mond nickel shot, and sponge-purity titanium* by vacuum melting in a zirconia crucible

Jan 1, 1963

By Walter H. Bruckner, George B. Clark

Since the end of World War 11 interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established conceming cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfonnance and more obtuse angles require thicker walls for the same base diameter. '. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, ten-sile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45" cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By Roswell H. Johnson

What becomes of the water which must have filled the oil and gas sands at the time of deposition, has long puzzled students of oil and gas and has found expression in Munn's well-known article on the hydraulic theory. Both Munn and Clapp have pointed out that in the Appalachian field the deeper sands carry increasingly less proportionate amounts of water. It seems to me probable that the principal source of oil and gas has been in the shales in proximity to the sands which now contain these products. The sand spits which mark off the lagoons from the sea comply particularly with the requirements of a limited sand imbedded in shales rich in organic matter. Cunningham Craig has objected to this view that the rich organic muds of lagoons are found only at the surface. That such muds do extend to considerable depth 1 am assured by Prof. Douglas W. Johnson, who has made an extensive study of the Atlantic Coast marshes. As any particular sand body becomes weighted by a heavier and heavier overburden, the result of increasing deposition, a part of the very large percentage of water in the uncompacted sand and mud is forced out. The water percentage of freshly settled mud is vastly higher than that of the resultant shales, or even of a very porous sand. If beds of less compressible material meet or underlie the shales in question, there will frequently be a lateral motion along such beds to some point where the upward movement will be resumed. We find in our laboratory work here that oil, gas, and water have extremely slight capacity for gravitational sorting while in a state of rest, but when moving the gravitational sorting is readily accomplished. As the oil, gas, and water pass a body of larger pores, the gas, owing to its lack of capillary attraction, is retained in the large pores. This has been predicted by Washburne, Blatehley and others on the ground that the water has a higher capillarity and grips the finer pores in such a way that there will be a greater proportion of oil and gas in the large

Jan 1, 1915

By R. K. Hopkins

For a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950" to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as —75" F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But, when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service. A great deal of credit is due to the members of the Boiler Code Committee and also to the members of the Joint A.P.I.-A.S.M.E. Committee, who have formulated codes that insure the safety of the

Jan 1, 1935

By Royal B. Jackman, Carle R. Hayward

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investigations. The development of X-ray examination of minerals and improvement in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investigators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation. Conclusions of Previous Investigators Various important conclusions reached by previous investigators are summarized in the following paragraphs, arranged chronologically. William A. Heywood:3 Slag losses increase with grade of matte but with the same grade of matte losses decrease as the acidity of the slag increases. Lewis T. Wright:' Slag losses are only partly due to prills of matte. It is suggested that part of the copper is dissolved in the slag. J. Parke Channing9 A considerable part of the copper enters the slag as silicate or oxide and not as sulfide. C. A. Grabill:6 Slag losses are both physical and chemical. Physical losses, due to poor settling, gas flotation and slight differences in specific gravity, are small under normal conditions. Chemical losses may- be due to formation of oxides or to solution of metals and sulfides. The last is considered the most important. John W. James:' The copper in converter slag is largely the oxide and as such enters the reverberatory slag when converter slag is added to the charge.

Jan 1, 1934

By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By Philip D. Pearson

CALAND Ore Co.'s dredging program has reached the halfway mark. The goal is to remove more than 160 million cu yd of lake bottom material overlying the iron orebody in Falls Bay of Steep Rock Lake, Ont. Two large dredges were constructed to remove this overburden, a layer of soil about 90 pct varved clay some 400 ft thick. Moisture content of the clay is high-approximately at the liquid limit of the soil. A few years ago, searching for additional reserves of ore, Inland Steel Co. looked toward Canada and the newly developed Steep Rock iron range. To this end an option agreement was signed Dec. 30, 1949, between Steep Rock Mines Ltd. and Caland Ore Co. Ltd., a wholly owned subsidiary of Inland Steel. Several drilling programs were conducted between this date and Jan. 1, 1953, when a 99-year lease was signed covering an area of 1249 acres. This lease calls for ore production to begin in 1960, with full production of 3 million tons per year by 1969.

Jan 8, 1957

By George W. Bain

Some problems concomitant with commercial exploitalion of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service department wants defects rectified and the cause determined to avoid recurrence The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character. Geological Problems The geological problems deal almost exclusively with the size of blocks. Size across the deposit is limited by thickness of individual beds. and along the strike by the space between crosscutting joints. Frequently the vertical depth of a block is reduced by exfoliation shells arising from spontaneous expansion. All these factors require consideration in developing a deposit to fill an order. Thickening of Marble Beds The limestone beds that became the marble deposits of the northern Appalachians and of the Yule locality in Colorado were seldom homo-

Jan 1, 1941

By C. C. Harris

The modern flotation machine is the result of decades of adaptation to a changing environment. In response to falling ore grades, and rising demands, tonnages, and costs, attempts are now underway to expand machine capacity by about an order of magnitude, while at the same time maintaining metallurgical performance and if possible reducing power requirements per unit throughput. Empiricism and rule-of-thumb have guided flotation machine design and scale-up, and a current need is for the development of a fundamental understanding of the subject. Design features of current and some obsolete machines are discussed in an attempt to outline those principles of flotation machine design which are known, and to delineate topics needing investigation. Attempts are made to distinguish between essential machine features required by the physics of the process, those features resulting from speculative theories on the flotation mechanisms, and features which are essentially styling variations. Topics discussed include: flotation mechanisms; tank and impeller/ stator design and dimensions; impeller speed; aeration; power consumption; particle suspension and dispersion; capacity; correlation of design parameters and operating variables; scale-up and scale-down; materials flow; problems in machine design. Design details and operating data for several current machine families are provided in Appendices.

Jan 1, 1976

By John W. Chandler

INTRODUCTION Where and how to spend the exploration dollar to net the greatest economic return, has always been a major problem for mining companies. Minerals are being consumed in ever increasing quantitie: throughout the world and the mining industry is being called on to meet this demand. In view of the present world-wide nationalistic trend, it is becoming more difficult to determine where exploration money can be spent most profitably. An exploration project should be evaluated continually--in the beginning, to define economic targets and later to determine, as early as possible, whether a project has a chance of developing into a venture that will make a profit acceptable to top management. At this point, a decision can be made whether or not to proceed with plans to bring in a new mine. Exploration, evaluation, and development, therefore, must be fully integrated in transforming an exploration project into a profitable mining venture. DEMAND FOR LEAD AND ZINC Lead and zinc are metals basic to our economy and the demand for them will continue to rise as the population in the world increases. If the population continues to grow at the present rate, it will about double by the year 2000. The accelerating demand for these metals is shown by statistics. Nearly half as much lead (48%) and more than half as much zinc (55%) have been mined between the two world wars as in all pre- ceding history. (1)

Jan 1, 1970

By G. R. Speich, S. A. Kulin

The isothermal formation of martensite at subzero temperatures has been studied in an austenitic stainless steel. The amount of martensite formed isothermally in a given time was found to follow a C-curve behavior with decreasing temperature. Since isothermal rnartensitic transformation occurs at temperatures above the true M. temperature of the olloy, the observed M. temperature is dependent on the cooling rate. It is believed that a general martensite theory must include the basic concepts of the strain embryo theory, and also the important role of thermal fluctuations. UNTIL recently the isothermal component of the martensitic transformation had been considered as a trivial effect in theoretical considerations of this type of transformation. One of the postulates used in defining a martensitic transformation was that the reaction was temperature dependent but not time dependent. Cohen and his associates1'2 were the first to report the isothermal formation of mar-tensite. They obsel-ved the time dependency of the martensite reaction at room temperature in plain carbon steels and certain tool steels. They found that a small amount of additional transformation occurred after the specimen reached the quenching temperature and that the rate of this isothermal transformation decreased rapidly with time. These authors considered this phenomenon to be a "tailing-off" of the main athermal reaction. Kurdjumov and MaksimovaL 5 studied the isothermal formation of martensite at subatmospheric temperatures in steels containing 0.6 pct C-6 pct Mn, 1.6 pct C, and in an iron-base alloy containing 23 pct Ni and 3.4 pct Mn. In each case it was found that both the initial rate and the total amount of isothermal transformation exhibited sharp maxima with decreasing temperature. They stated that it was possible to completely suppress the martensitic transformation in the 0.6 pct C-6 pct Mn steel by drastic quenching in liquid nitrogen. They interpreted their results in terms of a thermally activated process. The maximum in the rate of nucleation vs. temperature curve was assumed to be a result of the temperature dependence of the rate of growth of the martensite plates. It has been demonstrated," however, that martensite plates can form with great rapidity even at temperatures approaching absolute zero. In addition," attempts to confirm the reported suppression of the martensitic transformation by rapid cooling of a 0.6 pct C-6 pct Mn steel have proved unsuccessful. On this basis, and on other theoretical grounds, the validity of some of Kurd-jumov's results and conclusions is open to serious question. Cohen, Machlin, and Paranjpe' have proposed a theory of martensite formation based on the nucleation of strain embryos and a growth mechanism involving cooperative atomic displacements. According to this theory thermal fluctuations can make a strain embryo supercritical and thereby produce martensite isothermally. Das Gupta and Lement' have investigated the isothermal formation of martensite in a 17 pct Cr-0.7 pct C steel at temperatures below the ambient. They found that partial suppression of the martensitic reaction occurred on quenching into liquid nitrogen. That part of the reaction which can be suppressed is taken to correspond to the isothermal rather than the athermal part of the rnartensitic transformation. The initial rate of isothermal transformation for this steel was found to go through a maximum with decreasing temperature. This is in conformity with the findings of Kurdjumov and Maksimova for the steels used in their investigation. Das Gupta and Lement conclude that isothermal martensite formation occurs by the nucleation of new plates and is always preceded by some athermal transformation. An iron-base alloy containing 14 pct Cr-9 pct Ni was used in this investigation to study further the kinetics of the austenite to martensite transforma-

Jan 1, 1953

By P. V. Faragher

A metal or alloy finds its place in commerce in proportion to its ability to serve certain purposes better and more economically than other materials. While there is some overlapping of the fields of application of the various metals under discussion in this symposium, each one has its uses for which it is especially adapted. While aluminum is the most recent of the metals to enter the field, the development of the industry has been based on its peculiar properties, by virtue of which new uses for non-ferrous metals have been created. There has been substitution of this new metal for other members of the group but there has been a far greater development in entirely new fields. In common with the other non-ferrous metals, aluminum is resistant to atmospheric corrosion. It also withstands the action of many of the common chemical reagents, strongly alkaline substances being the notable exceptions. The outstanding properties on which the application of aluminum is based are its low specific gravity and its ease of fabrication into the forms in which it is used. It is noteworthy that this property of specific lightness is retained in all the commercial aluminum-base alloys. This statement does not apply to aluminum bronze; this is more properly a copper-base alloy, since aluminum enters into its composition to the extent of only about 10 per cent. None of the commercial casting alloys of aluminum has a density exceeding that of the parent metal by more than about 10 per cent., and some are actually lighter. In the so-called "strong alloys" of aluminum in which strengths comparable to that of mild steel are developed by heat treatment, the greatest increase in density is only slightly more than 3 per cent., and one of these, also, is lighter than aluminum. This property of lightness combined with the desirable mechanical properties of the alloys, makes aluminum especially suited for parts of moving assemblies where saving in power, as well as a decrease in stresses resulting from inertia and vibration, are of importance.

By Hugh M. Roberts, R. D. Longyear

Introduction ............................ 27 GEnERal Geology........................... 29 The ORebodY in Western Falco~ridgI TownsRip........... 31 Quartzite-Graywacke Formation................... 33 Greenstone............................ 33 Norite ............................. 33 Metamorphism.......................... 35 The Orebody........................... 36 Mineralogy ........................... 37 Grade of Ore........................... 42 Genesis oF tEe Ores . :....................... 43 Summary of Various Hypotheses.................. 44 Magmatic Segregation by Crystallization of Sulphides........ 44 Gravitational Segregation of Molten Sulphides at the Base of the Magma 45 Intrusion of Molten Sulphides after the Consolidation of 'he Nurite.. 45 Deposition by Hydrothermal Solutions.............. 46 Magmatic Segregation by Extraction from Crystallizing Norite... SO The Relationship between the Exploration and Theories of Origin .... 50 Volume Relations of Norite and Sulphides............... 62 Intimate Association of Norite and Sulphides............. 53 Granitic Material........................ 54 Uniform Content........................ 54 Sulphides in Walls......................... 54 Absence of Typical Hydrothermal Minerals.............. 55 SUmmaRY................................ 56 Introduction During 1916 and 1917. the E. J. Longyear Co. of Minneapolis. Minn., carried out a campaign of exploration for nickel-copper ore in the Sudbury District of Ontario. The work was initiated by W. E. Smith. a resident of Sudbury. who called the attention of W. J. Mead. Chief Geologist

Jan 1, 1918

TWO recent developments in open hearth steelmaking have had a substantial impact on metallurgical practices and operating procedures. These are: (1) the use of oxygen roof lances for accelerating the refining reactions, and (2) the use of a spring-arch, basic roof for prolonging the life of the furnace. Although these practices can be used separately, they are generally used to complement each other in an effort to obtain minimum heat time consistent with an acceptable rate of wear of the refractory roof, walls and port ends. DECARBONIZATION BY OXYGEN INJECTION The use of oxygen to speed carbon elimination was perceived by Sir Henry Bessmer but its practical use in steelmaking could not be realized until processes were developed for the manufacture of low cost, tonnage oxygen. However, as early as 1922 Bigge1 obtained a patent covering the use of gaseous oxygen to speed decarbonization of a molten steel bath. At that time, oxygen was available only in bottles and at a cost of $240 per net ton. At the end of World War II the price of oxygen had dropped to $80 per net ton, and as a result, metallurgical oxygen (99.5 per cent began to come into widespread experimental use for decarbonization in open hearth and electric furnace shops.2-8 Even this price prevented oxygen's routine use for other than decarbonizing the bath in shops producing substantial quantities of steels containing less than 0.40 per cent carbon. Today, tonnage metallurgical oxygen can be manufactured for less than $15 per net ton, and commercial purity oxygen (95 per cent is reported to cost less than $5 per ton. Thus, it is not at all surprising to find many open hearth shops effectively using large quantities of oxygen to accelerate decarbonization. Equipment for Oxygen Injection. The oxygen may be injected by a lance pipe inserted through the wicket hole and pushed several inches into the steel bath, or by a water-cooled jet inserted through the back- wall, endwall, or roof, and immersed in the slag or set just a few inches above the slag. Oxygen at approximately 100 psi is piped directly to control stations adjacent to each furnace. The installations should include adequate safety devices such as fire checks and emergency valves,

Jan 1, 1964

By W. H. Emmons

Most mineral deposits change as they are followed downward on their dips. Some of these changes are due to primary arrangement; different ores were precipitated at different depths when the deposits were formed. Other changes are due to weathering or secondary enrichment. The chief changes resulting from weathering, in the main, are understood and standard changes are recognized. The processes are relatively simple. They take place at ordinary temperatures and pressures and can be duplicated in the laboratories. Moreover, there are thousands of deposits available for study, because the processes take place near the surface where the development of mines is begun. The changes due to primary arrangement of the deposits of the metals are not so well understood. Deposition has taken place at higher temperatures and our knowledge of the chemistry of the processes leaves much to he desired. Very few experimental data are available. The deposits, moreover, offer fewer examples because many mines are not developed to depths where the changes can be studied and a change to unprofitable material usually results in stopping work. Most students of ore deposits now accept, as confirmed, the hypothesis that nearly all lodes and related deposits were formed by solutions originating in intrusive igneous masses. Outward from these masses, the deposits at many places are grouped in zones and the arrangement noted from the intrusions outward are commonly the reverse of the changes noted from the surface downward in a single lode. A study of the changes in groups of deposits, from the parent intrusion outward, will throw light on the changes to be expected in a single lode downward. Recause the changes in series of deposits from the intrusive outward may all be observed near the surface, where more data are available, it is possible to increase the number of examples many fold and to apply the statisttical method of study with greater confidence of avoiding error. It is not everywhere possible to identify the parent igneous body to which a group of ore deposits are related. Several kinds of criteria are available; certain groups are superior to others. By applying the

Jan 1, 1924

KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

By C. G. Grant, Wm. B. Price

This investigation of low copper-nickel silvers was untiertaken to check the work of Lèon Guillet on special brasses and to determine, more accurately, the effect of the addition of nickel on the mierostructure of the binary alloys of copper arid zinc. It was hoped that the results could be successfully applied to the practical production of low copper-nickel silvers. To explain the results of his investigations on special brasses, Lèon Guillet evolved his conception of "fictitious compositions." He states,' in his general conclusions, that on the introduction of a small amount of a third metal to a copper-zinc alloy, it enters into solid solution with the normal constituents up to saturation, but by so doing it brings the ternary alloy into a state microscopically equivalent to a binary copper-zinc alloy of fictitious composition, and physically more nearly like the latter than the brass containing copper-zinc in the ratio actually present. The physical properties of the ternary alloy, when compared to the same properties of an actual brass of the fictitious composition, are modified by the natural properties of the third element. Beyond the point of saturation, a special constituent appears and the above generalization no longer holds. For example, if a 60:40 brass has 4 per cent. of tin substituted for 4 per cent. of zinc, the actual composition would analyze 60:36:4. Assuming that 1 per cent. of tin plays the same part as 2 per cent. of zinc, the proportions of copper and equivalent zinc may be stated as 60 parts of copper and 44 parts of zinc, which, figured to 100 per cent., gives an analysis of 57.7 per cent. of copper and 42.3 per cent. of zinc, the fictitious composition for a 60:36:4 tin brass. The relation between ternary alloys containing copper and zinc together with a third metal, and the microscopically equivalent binary alloy of copper and zinc, may be expressed mathematically.

Jan 1, 1924

By John Wulff, J. H. Hollomon

The opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was re-deposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,a in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As2O3),

Jan 1, 1942

By Lars Thomassen, Ernest Kirkendall, Clair Upthegrove

THE amount of research done in the last few years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Desch1 in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl's paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for its review and bibliography is an article by A. I. Krynitsky.3 While considerable material has appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined at three temperatures. PROCEDURE The method used consisted of plating copper on a beta brass, heating it to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the temperature at which diffusion takes place the beta brass is saturated with copper. Thus, while the beta brass supplies the zinc, no diffusion takes

Jan 1, 1938

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father ¬Dr. Samuel Gridley Howe, his mother-Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature. is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass . . . by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works "f the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942