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IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman. A. A. STEVENSON, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, William Kelly, J. S. Unger, William H. Blauvelt, Charles Kirchhoff, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph W. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. J. E. Johnson, Jr.,

Jan 1, 1914

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By Scott Howard

MANGANESE being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Ar3 transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the Ar3 transformation occurs at a temperature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3 quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Ar3 point as falling to 0° C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer,2 using alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 percent for the manganese content at which Ar3 is depressed to 0° C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By C. S. Smith, W. M. Williams

THE quantitative study of grain shape in three dimensions has been a difficult one from the practical standpoint. Experiments on grain shape have usually been based on indirect observations of two-dimensional metallographic samples or on grains separated by intergranular corrosion or fracture. The latter method was used in particular by Deschl in 1919 in observing the shapes of ß-brass grains which had been separated with mercury. The similarity in detail of shape and packing that exists between bubbles in a soap froth and metal grains was noted by Desch who remarks that: "Surface tension has an. important share in determining the form of the crystal grains in a solidifying metal and such grains have a tendency to assume the shape of foam cells." More recently the relation between grain shape and grain growth has been studied by Harker and Parker.' The importance of surface tension forces in determining microstructure has been discussed by Smith," and an analysis of the topologi-cal rules that apply to such structures has been made by the same author.' Biologists have made valuable contributions to the general problem of shape and form in an assembly of space-filling cells subject to surface tension forces. Particular mention must be made of the extensive researches of Lewis5,8 on botanical and anatomical tissues, and Matzke and Nestler,7,8 who have made painstaking studies of bubble shapes in different kinds of foam. The present paper introduces a new method of studying individual grains in particular alloys—a method which may well find use in other metallurgical researches, and which seems also to be applicable in biological problems. Metal Grains in Three Dimensions The individual grains in a piece of metal or the bubbles in a soap froth must satisfy two conditions —they must be in juxtaposition so as to fill space and their interfaces must conform to the laws of surface tension. If a further restriction is imposed, namely, that only one type of polyhedron be used, then the sole possibility is an assembly of "minimal" tetrakaidecahedra," each polyhedron having eight doubly-curved hexagonal faces and six plane quadrilateral faces, the angles between adjacent faces being 120". Such cells could be stacked on a body-centered cubic lattice and would be quite stable. For many years it was believed that soap bubbles actually possessed the shape of this ideal body, and the hypothesis was the starting point for several investigations on the shapes of soap bubbles, biological cells, and metal grains. These investigations have shown, what might have been obvious in the beginning, that if the condition of symmetry is relaxed the tetrakaidecahedron is almost never found. If we retain only the rule that all contacts should be in local surface tension equilibrium and that the assembly should fill space, metal grains may then take a nearly infinite variety of shapes and no single one may be regarded as an archetype. These two conditions, which are fully discussed in one of the previously mentioned papers,' lead us to think of a typical grain in an annealed metal as having the following characteristics: 1—A grain may have any number of faces, but usually between nine and eighteen. The faces (each of which is, of course, shared by two grains in the assembly) may have any number of edges, but usually between four and six. Pentagons are by far the most frequent. 2—In the assembly of grains each edge is shared by three faces and by three grains. Each vertex is a point shared by four grains, six faces, and four

Jan 1, 1953

By P. A. Fisher, J. B. Wilson, D. J. Whitehead, C. J. P. Ball, A. C. Jessup

The properties of a new magnesium alloy ZT1 containing 3.0 pct Th, 2.5 pct Zn, 0.7 pct Zr are described. The alloy possesses good creep and fatigue resistance up to 650°F, is free from microporosity, and is readily sand-cast. ZT1 is shown to be superior to zinc-free Mg-Th-Zr alloys. THE advent of the jet engine created a demand for a light sand-casting alloy capable of being cast into large complex shapes and capable of resisting creep at temperatures up to 500°F. This demand has been largely met by alloys of the magnesium-cerium mischmetal-zirconium types, containing about 3 pct Ce mischmetal and 0.7 pct Zr, typified by Elektron magnesium alloys MCZ and ZREI, the latter alloy also having a zinc addition of 2.5 pct. These alloys utilize the valuable properties at elevated temperatures conferred by the addition of rare earth metals to magnesium, a fact which has been known for many years and discussed by several investigators.1-1 Murphy and Payne8 showed that the addition of the powerful grain-refining element zirconium to Mg-Ce mischmetal alloys produced alloys with attractive room temperature properties combined with good creep properties and castability. With the increasing power of modern jet engines the temperatures to which some of the magnesium parts are subject are likely to exceed the safe working range of the cerium-mischmetal-containing alloys, and at the beginning of the research considerable interest had been shown by aeroplane engine designers in a magnesium sand-casting alloy suitable for service at higher temperatures, e.g., 600°F and above. At an early stage in the development of this type of alloy a check on the fatigue properties at elevated temperatures indicated that, since the fatigue limit even at 108 eversals was appreciably higher than any permissible creep stress, the main emphasis of the research could be concentrated on creep behavior. The primary aim in developing the new alloy has therefore been to attain maximum creep resistance; but due consideration has also been given to other important properties such as castability, tensile strength, and cost. It is by now well established that it is not possible to correlate creep strength with other short time mechanical properties such as are obtained in tensile

Jan 1, 1954

By Rudolf Gahl

THE history of flotation in America is very short, at least as far as the large-scale application of the process is concerned. It is remarkable how many important developments have taken place inn the last few years and are already being extensively utilized. What was new a year ago, seems almost commonplace now. For this reason it is with hesitation that I follow the suggestion: of Dr. Ricketts, President of the Institute, to describe the experiences of the Inspiration Consolidated Copper Co. with the flotation process. TESTS CONDUCTED IN SMALL TEST-MILL When the Inspiration company first decided to build a concentrating plant, nothing was known about flotation, and the process was to be gravity concentration pure and simple. Demonstration Tests Conducted by Minerals Separation Co. While plans were being prepared by H. Kenyon Burch (who had been intrusted with the design and construction of the concentrator) the Minerals Separation Co., a concern at that time little known in America, asked and obtained permission to demonstrate the value of its flotation process for Inspiration ore. As. a consequence, a small 50-ton flotation machine of standard design was added to the company's test plant and started to operate in the beginning of 1913. This marks the beginning of flotation at Inspiration. The results obtained with this machine, which was operated by members of the Minerals Separation staff, so far surpassed what this company anticipated that it was decided to continue flotation tests for this purpose, and two of the flotation experts of the Minerals Separation Co., I. L. Greninger and G. A. Chapman, were retained. L. R. Wallace, now superintendent of the Miami works of the International Smelting Co., was at that time metallurgist of the Inspiration company and in that capacity took an active part' in these tests. Great credit is due to him for his quick recognition of the possibilities of flotation.

Jan 9, 1916

By Kent R. Van Horn, W. P. Sykes

Since Honda and Murakamil in 1918 proposed their constitutional diagram of the carbon-free iron-tungsten system, considerable effort has been expended by several investigators in attempts to define more positively the structural features of the alloys. The existence of an intermediate phase corresponding to the formula Fe3W2 (68.7 per cent W) was proposed from evidence of a purely metallographic nature by one of the present authors2 in 1926. Since that time the identity of this phase has been confirmed by Arnfelt3 and by Takeda,4 both of whom employed X-ray methods as well as the microscope and the chemical analysis of isolated microconstituents. According to Arnfelt, Fe3W2, as crystallized from the iron-rich melts at a temperature above 1450° C., contains by analysis 68.7 per cent W. The lattice of this phase is characterized by trigonal symmetry. Arnfelt, moreover, proposed a second intermediate phase formed at some temperature between 1450" and 1000" C. by a peritectoid reaction involving Fe3W2 and the iron-rich solid solution. A melt containing 25 per cent W was cooled to 1000" C. and heated for 100 hr. The precipitated tungsten-rich constituent was separated and found by analysis to contain 62.6 per cent W. This composition agrees closely with that represented by the formula Fe2W (62.2 per cent W). Diffraction patterns from the concentrated precipitate showed a hexagonal unit cell. Takeda confirmed the data of Arnfelt regarding Fe3W2 but was unable to detect Arnfelt's second intermediate phase. While Takeda failed to describe in detail the treatments employed, he stated that in alloys containing 40 per cent W which were quenched after heating at various temperatures between 1200" and 1450" C. no evidence of the second phase (Fe2W) was observed 'either in the microstructure or in the diffraction patterns of isolated residues. He therefore considered the existence of this low-temperature hexagonal compound as disproved.

Jan 1, 1933

By Frederic E. Carter

There have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it was not known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there were noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals were meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20 lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K'l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 ' at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K'1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken's10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- ', and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By A. H. Hand

When considering the question of future demand for crude petroleum in California, one must first decide whether it is to be approached in the light of the definition of "demand" when used in economics; i.e., "The quantity of any commodity required or sought in the market," or in the light of markets developed to dispose of total supply. Therefore, is the California demand of future years to be predicated on a continuation of supplying markets developed following the surplus production commencing in 1922, or predicated on supplying what would be termed economic markets ? If the latter, what are economic markets ? Obviously, the Pacific Coast States and Canada, Alaska, Hawaii and probably the Pacific side of Central and South America, can be considered as normal markets for California petroleum products. While there have been small quantities of gasoline shipped into the PacSc Coast from East Texas, transportation costs, plus import taxes in the case of foreign oil, are a sufficient barrier to justify considering that these markets will be retained. But how about our participation in Atlantic and Pacific foreign and intercoastal markets? During the five years preceding 1931 California shipped substantial quantities of gasoline to the United Kingdom and to France, Germany and Italy. During recent years our business in European markets has been restricted to occasional shipments of gasoline and Kettleman crude. This loss of business is occasioned by the development of production in the Mid-Continent, principally East Texas, and in Iraq, Rumania, Venezuela and other closer producing areas, which makes it impossible at the prevailing crude-oil prices for California to be competitive in supplying any substantial portion of these markets. It is therefore apparent that under a stabilized price structure that will return the California producer a reasonable price for his oil, future Atlantic foreign -business will be restricted to occasional spot cargo sales. As to Pacific foreign shipments which, in addition to Central and South America, consist principally of shipments to Japan, China, Australia and New Zealand: A considerable portion of the business we had with Australia and New Zealand until four or five years ago is now being

Jan 1, 1937

By W. O. Borcherdt

THE 650-ton underground mill of The Empire Zinc Company of Colorado (a subsidiary of The New Jersey Zinc Co.) serves the Eagle mine at Gilman in the Battle Mountain mining district of Colorado, The topography is rough, the mine and mill being under Battle Mountain and the adit entrance in the north wall of the canyon of the Eagle River, which is here a steep gorge. The town of Gilman stands on a shoulder of the mountain at altitude 8975 ft., above sea level, along the Pike's Peak ocean to ocean highway and contains the company office and the usual facilities of a modern mining town. The railway contact is at Belden, altitude 8370 ft., at the bottom of the gorge directly below Gilman, where the westbound track of the Denver and Rio Grande Western Railroad is cut along the north bank and the eastbound track along the south bank of the river. A general description of the mine, mill and service facilities, with an account of the geology, character of the ore and methods of mining and milling having previously been published in a series of articles1, this paper will discuss with as little repetition as practicable the reasons for building the mill underground rather than as a conventional structure, the methods of construction employed and the experiences gained in what is apparently the pioneer plant of this type and extent. There is a large historical background for underground plant construction. From the dim past caves have been used for dwellings, stables, storage and shops. It was natural that where caves were available their many advantages led to their enlargement to suit convenience and where they were not available but the ground conditions, topography and drainage were favorable, to the construction of artificial caves. In the vicinity of Epernay, France, extensive underground chambers protect the manufacture and storage of champagne-an intricate and ingenious application of chemical engineering-and in recent years these plants have been mechanized by the installation of conveyor systems. In the

Jan 1, 1937

By M. H. Loveman

The orebody described below has been rediscovered and developed within the last 3 years. It has, however, been known and worked by the Chinese for hundreds of years. When assay values and size are considered, it contains what is probably one of the largest single bodies of zinc and lead sulphides yet found. The tonnages developed at other places, as at Broken Hill, are much greater but the average zinc and lead sulphide contents are considerably lower than at Bawdwin. Bawdwin is situated in the semi-independent State of Tawng Peng, one of the numerous units which make up the Northern Shan States. These States are under British rule and are generally considered as a portion of Burma. They are governed as a separate administrative unit, however, under the Lieutenant Governor of Burma. Each State is under its own chief, or Sawbwa, who has considerable power over his own subjects. Bawdwin is approximately in latitude N 23°6', longitude E 97°201, about 50 miles south of the nearest point on the Chinese border and 450 miles north of Rangoon (Fig. 1). The period at which mining was first begun at Bawdwin is unknown. The most reliable records have been obtained by deciphering local Chinese inscriptions and from these it is concluded that the work dates back to at least the beginning of the 15th century. The first undoubted reference to the mines by a European is by Syrnes in 1795. Crawford in 1827 estimated the output of silver from the mines at $600,000 anually. At about the middle of the 19th century the rebellion of the Chinese Mohammedans in the neighboring Chinese province of Yunnan so weakened the power of the Chinese that the incursions of hostile tribes (Kachins) made work extremely dangerous. The mines were finally abandoned by the Chinese about 1868. The . closing down of the mines was probably not entirely due to outside causes but may have been influenced somewhat by the increasing difficulty of handling the water, as the workings gradually descended below the water level of the district. Several attempts were made by the Burmese kings, Mindon Min and Thebaw, to resume operations, but because of a

Jan 1, 1917

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By Arthur Dwight

ARTHUR SMITH DWIGHT, president of the American Institute of Mining and Metallurgical Engineers, was born in Taunton, Mass., on March 18, 1864. He is descended on both sides from early settlers, one of whom was Richard Warren, of the "Mayflower." His forebears included Col. Benjamin Church, Tim-othy Dwight, and the Rev. Jonathan Edwards, third president of Princeton College. Mr. Dwight was graduated in 1882 from the Poly-technic Institute of Brooklyn, N. Y., and three years later from the Columbia School of Mines, with the degree of Engineer of Mines. In 1914, he received the honorary degree of Master of Science from Columbia. On leaving Columbia in 1885, he went to Pueblo, Col., and for thirteen years was associated with the Colorado Smelting Co. Beginning as assayer he rose to be general superintendent. When he gave up the latter position he became connected with several large companies in the mining and smelting of lead, copper and the precious metals in the Rocky Mountain region. This work occupied him from 1897 to 1906, and six years of that time were spent in Mexico. He was general manager of the Greene Consolidated Copper Company at Cananea, Mexico, in 1906, when trouble first developed against the régime of Diaz. A general uprising was planned to seize the mines, and with money and supplies so obtained, carry the revolt through the interior. Mr. Dwight turned his industrial organiza-tion into a military unit almost over night, stemmed the tide of revolution, and had the situation well in hand before the arrival of troops. In the fall of 1906 he returned to New York and began practice as a consulting mining and metallurgical engineer. He next developed important metallurgical patents for the roasting and agglomeration of fine ores, known as the Dwight and Lloyd sintering process, now extensively used ail over the world.

Jan 3, 1922

By Carl Zapffe

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

Jan 1, 1927

By F. H. Wilson, M. L. Kronberg

The low temperature recrystalliza-tion of very heavily rolled copper produces a fine grained structure with a high degree of preferred orientation. Additional heating to within a few hundred degrees of the melting point may induce an abrupt and pronounced increase in the grain size, with the resulting crystals having new orientations. This behavior at high temperatures is commonly termed "secondary recrystallization." Several investigations have dealt with the phenomenon arid have served to bare many features of the beha~ior.1-4 In general,observations have been made on the sizes and shapes of the grains, and data have been presented showing the existence of an induction period in isothermal experiments. Although it has been well established that the orientation before the change is statistically (100) 10011, the so-called "cubically aligned" texture, there is no such agreement on the orientation after the change. For example, Dahl and Pawlek1 describe it as being equivalent to an approximately 30" rotation about the [l00] axis of the ideal cubic texture which is parallel to the rolling direction, the resulting orientation being near (210)[001]; and Cook and Richards2 find an orientation of approximately (110)[L12]. Since the completion of most of the work to be reported in this paper, Rowles and Boas3 have published their ver] illuminating paper on "secondary recrystallization," in which they present convincing evidence for a third orientation and show that their esperiments give no evidence for either of the other two orientations. The orientation is described as equivalent to an approximately 30° rotation about a [ 111] pole of the ideal cubic orientation. The existence of a variety of reported orientations is not unique for copper, for a similar state of affairs exists for other systems that have been studied— aluminum, nickel, nickel-iron alloys, and others. It seems therefore that the existence of this variety does not necessarily constitute a contradiction, but rather indicates that different experimental conditions yield different results. The fundamental nature of the phenomenon has not been elucidated. However, it has been generally recognized that the large grains could be the end product of growth of a few select grains already existing in the sample in minor amounts—too small to allow detection—or that entirely new ones could be formed by a process of nu-cleation and growth. Existing experimental evidence does not distinguish between these two most apparent possibilities. Nevertheless, the former has been more generally favored largely because our current understanding of the state of an annealed metal has not made it seem reasonable to expect a nucleation event to occur at temperatures above those required for the primary recrystallization. Observations on the Preparation and Heating of Twin-bearing Cubically Aligned Copper The starting material used throughout. the investigation was a bar of OFHC copper, forged and annealed at 950°C. Visual inspection showed the grain size to be around 0.5 mm, and did not disclose any preferred orientation. A chemical analysis showed the following composition: Cu + Ag— 99.99 Pct S — 0.005 pct 0 — <0.005 pct For the preparation of cubically aligned copper, ¾ in. thick slabs were cut from the bar, heavily pickled in concentrated HNO3 and cold rolled to sheets about 0.012 in. thick. The reduction in thickness was approximately 98.5 pct. Standardized annealing techniques were followed. Samples to be heated were lightly dusted with alumina in order to prevent sticking and then sandwiched between 1/16 in. copper plates. The resulting sandwich was heavily wrapped with copper sheet, and then annealed in air. The protection was such that only very thin films of oxide were formed. That the associated light oxidation of the samples had no specific effect on the recrystallization behavior was shown by the similar results that could be obtained on annealing in highly purified and dried hydrogen. Two methods were used in bringing samples to temperature: (1) by placing the package directly in the furnace at temperature and (2) by placing the package in the furnace at room temperature, and then slowly increasing the temperature. The corresponding heating rates are illustrated in Fig 1, and will be referred to as "rapid" and "slow," respectively. Unless specified otherwise, all anneals will be of the former type. Metallographic examination was made on samples prepared by electrolytic polishing and etching as described in the Metals Handhook.* STRUCTURES FOUND BEFORE "SECONDARY RECRYSTALLIZATION" OCCURS Annealing the rolled material for 1 hr at 400°C produced a heavily twinned, cubically aligned structure, the grain size being of the order of 0.03

Jan 1, 1950

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By J. T. Crawford

ALTHOUGH nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal briquetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the worlds largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis. water-front and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned. GENERAL HISTORY In the summer of 1871 a small sailing vessel entered the harbor of Duluth Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1948