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By H. K. Work

The Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of stccl-making are partly economic and partly metallurgical.1 In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect—it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Ressemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (1) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. The Control Problem In this day of scientific control of technical processes, where the operating

Jan 1, 1941

By David Mitchell

THE production of fluorspar is one of the smaller nonmetallic indus-tries in the United States with a capital investment-about $10,000,000. Shipments from United States mines' in 1936 totaled 176,231 short tons valued at $3,111,268, an average price of $17.65 per ton. The United States produces about 40 per cent of the world's fluorspar, of which about 90 per cent comes from the Illinois and Kentucky deposits along the Ohio River.2 Further detailed information on the fluorspar industry in the United States is given by Hatmaker and Davis.28 Fluorspar is marketed according to the following relative quantities and specifications: Consump- Specifications, Per Cent Use Form tion in 1936, Per Cent CaF2 SiO2 Fe2O3 Metallurgical Gravel 79 +85 -5 or lump Ceramic,. Ground 10 +95 -3 -0,1 Acid Ground 11 +98 -1 The concentration of the coarser sizes presents relatively little diffi-culty, good recoveries being obtained with jigs and tables. However, sizes smaller than about 10 mesh cannot be successfully treated by ordinary gravity separation methods and so have been accumulating as

Jan 1, 1938

Jan 1, 1968

By Donald Barton

THE theory of gravitation is based on Newton's law that any two bodies exert a mutual attraction which is proportional to the product of their masses and inversely proportional to the square of the distance between them; i. e., A =KRM/R2 (1) where K is a constant, M and m are the respective masses of the two bodies, and R the distance between them. In the earth's gravitational system, the earth is one of the bodies; the other may be any body within or without the earth. In theoretical dis¬cussions and calculations in regard to gravity, that other body usually is taken as a unit of mass: in the C. G. S. system, a body of one gram in mass. GRAVITY AND LEVEL SURFACES Gravity is defined in geophysics as the force of attraction exerted by the earth, towards itself, on a body of unit mass. The intensity of gravity is usually expressed in dynes of force or in centimeters of acceleration. In geophysical work in America, most commonly it is expressed in dynes (per gram) with the "per gram" understood and not directly expressed. In geophysical work in Europe, most commonly it is expressed in centimeters per second per second (cm./sec.2) and less commonly merely as centimeter-gram-second units (C. G. S.). At sea level, the intensity of gravity amounts very nearly to 980 dynes. The vertical is the direction along which the attraction of gravity is exerted at any point. . In most cases, it is very nearly, but not quite, per¬pendicular to the earth's surface. The path that would be taken by a body falling freely through space toward the earth is vertical at each point and may be spoken of also as "the vertical," or as the line of the vertical, or as a line of force of gravity. At the earth's surface it com¬monly is very nearly, but not quite, a straight line.

Jan 1, 1928

Jan 1, 1924

By William Alden

A GREAT landslide occurred on June 23, 1925, in the valley of Gros Ventre River, about 35 miles south of Yellowstone National Park (Fig. 1). The relations of the north-easterly dipping rock formations of the slide scarp and of the dam formed by the slide are shown in the diagrammatic cross-section of the valley (Fig. 2). This generalized section is based on unpublished maps and notes by Eliot Blackwelder, in the files of the U. S. Geological Survey. FIG. 1.-MAP SHOWING SCARP AND DAM (LARGE DOTS) AND LAKE (CROSS-LINED) FORMED BY LANDSLIDE BLOCKING GROS VENTRE RIVER. (Scale 1, in. = 1 mile; contour interval 100 ft. From Grand Teton and Mt. Leidy topographic maps). Heavy rains and melting snow in the Gros Ventre Mountains had saturated clay layers in the Carboniferous strata, which dip toward the valley at angles of 18° to 21°, consequently an enormous mass of rock at the end of the north spur of Sheep Mountain became loosened and, on the afternoon of June 23, slid suddenly down into the valley. Within a few minutes this mass of debris-estimated as 50,000,000 cu. yd.-carrying

Jan 1, 1928

By S. L. Payne, J. P. Morris, R. L. Kipp, G. R. Zellars

The activities of iron and nickel in liquid Fe-Ni alloys were determined by measuring the vapor pressures of iron and nickel above the alloys and comparing with the vapor pressures of the pure metals. Nickel was found to deviate negatively from Raoult's law over the entire composition range. Iron behaves ideally down to 0.7 mole fraction but shows negative deviations at lower concentrations. At 1600°C the activity coefficients at infinite dilution are 0.40 for iron and 0.66 for nickel. 1 HE formulation of the conditions of chemical equilibrium between liquid metals and gases or slags is an important application of thermodynamics to pro- cess metallurgy. Usually the metal and slag phases are solutions of several components; and for accurate calculations, it is often necessary to use the activities of the components in place of their concentrations. Data concerning activities, however, are quite meager. The evaluation of the activities of iron and nickel, presented in this paper, is part of a project to determine activities in iron alloys at elevated temperatures.

Jan 1, 1960

By G. Horvay, J. G. Henzel

Nomograms and charts are provided which permit rapid determination of the mold-casting interFace temperature and the speed of solidification when a semiinfinite ingot is cast into a semiinfinite mold. The physical properties of the mold, the frozen metal, and the liquid metal are not assumed to be equal, but they are assumed to be temperature independent. The results are correlated with charts prepared by Paschkis and Hlinka—using Columbia University's Analog Computer—for the freezing of finite ingot slabs when a constant surface temperature is impressed, and with experimental cooling curves obtained by Pellini in sand and iron molds for 7 in.-sq steel castings. x = coordinate directed to right of zero (freezing direction) y = coordinate directed to left of zero (melting direction) e = position of freezing front (in x direction) ? = position of melting front (in y direction) $ = temperature (function of position and time) ? = fixed temperature 2L = width of finite slab Y = a fixed position in the semiinfinite mold, or the width of a finite mold (see Section 7) Properties y = density, lb per cu ft c = specific heat, Btu per lb deg F k = conductivity, Btu per ft hr deg F X = heat of fusion, Btu per lb k = k/Yc = temperature diffusivity, sq ft per hr* b - = = - heat diffusivity, Btu per sq ft deg F Vhr Subscripts 2 = pertaining to the still-liquid metal (case of freezing), or the medium which furnishes the heat (case of melting) 1 = pertaining to solidified metal (case of freezing), or to molten metal (case of melting)* 0 = pertaining to mold (case of freezing), or to the still-solid metal (case of melting) f = pertaining to fusion condition (eg.,?f - fusion temperature) i = pertaining to the location x = 0 (the mold-ingot "interface")

Jan 1, 1960

By Wm. Reuben Webster

BRASS is an alloy of copper and zinc. The brasses (using this term to denote all useful proportions of the two constituents) are the most valuable and widely employed of all [ ] nonferrous alloys, because of their high resistance to ordinary corrosive agencies and the very wide range of properties that may be imparted to them by variations in the proportions of the constituents and by variations in mechanical treatment and heat-treatment. Fig. I shows the normal physical properties, as determined by standard tensile tests, of the series when in the annealed condition. Fig. 2 shows the effect of varying amounts of cold-working on an almost pure brass containing 70 per cent copper and 30 per cent zinc. Fig. 3 shows the effect of annealing at various temperatures on the same alloy. This effect is somewhat modi [ ] fled by the degree of cold-working to which a brass has been subjected, as shown by Fig. 4. A fourth test, which is empirical, has been found useful because of its simplicity -the hot hammer test. Samples Y2 in. in diameter and ¾ in. long are placed in a suitable furnace. These are withdrawn one at a time at successively higher tempera¬tures and are subjected to the blow of a drop hammer weighing 50 lb. with a drop of 4 ft. The percentages of' reduction in length of the cylinders are plotted against temperatures and give a comparative measure of plasticity at different temperatures. The results of this test on several

Jan 1, 1942

By C. R. Bailey, H. F. Dunlap, Ellis Shuler, H. L. Bilhartz

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent 'saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge's paper.' In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01' the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949

By George C. Reynolds

INTRODUCTION The overall importance of the minerals industry during the next 20 years was highlighted In "The Global 200 Report to the President" (Barney, 1982) in the following terms: "The industrial and agricultural processes that are taken for granted today would be severely disrupted of any one of dozens of critical minerals ceased to be available in dependable, reasonably priced supply. Supply in turn has become highly energy intensive and international In scope ...... because resources are not uniformly distributed geographically, political considerations (also) become an Important determinant of price and trade patterns." In attempting to determine Australia’s contribution of bauxite raw materials to the world of the future, this paper necessarily also concerns itself with the alumina and aluminium industry to which it supplles the raw material. It is an industry which is energy intensive, International in scope and heavily influenced by political considerations. The aluminium industry has shown a remarkably rapid growth during the past 20 years (Fig. 1).

Jan 1, 1982

By Rudolph Emmel

THE mines operated by the South American Development Co. are located in the Zaruma mining district of southwestern Ecuador. They are near the old mining town of Zaruma, which is the only important city in the canton of the same name. The district is situated in the upper end of a valley lying between two spurs of the Cordillera, one of which may be considered the Coast Range and the other an intermediate range. The mining camp proper, known as Portovelo, and the plant are 2.4 km. south of Zaruma, on the north bank of the Amarillo River, a tributary of the Tumbes River, which flows southwestward through Peru to the Pacific. Portovelo is difficult of access; it is reached from Guayaquil by means of river steamers and muleback. Embarking at Guayaquil, the route is down the Guayas River, across the Jambeli Canal, and up the Santa Rosa River to Santa Rosa, a distance of 177 km. From Santa Rosa, the road or trail follows the Santa Rosa River, then across the summit of the Coast Range into Portovelo, a distance of 74 km.-a two-day trip on muleback. The mining property of the South American Development Co. comprises 297 lode claims and 142 placer claims. The combined lode claims cover an area, roughly rectangular in shape, 9000 m. long from north to south by 4000 m. wide; the northern edge of the rectangle is about 3000 m. north of the central plaza of Zaruma. Mineral lands in Ecuador are held by virtue of an annual tax per claim paid to the central government, no surface rights being included.

Jan 1, 1925

By Leon Eliel

TEN years ago .a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these. isolated bits of infor-mation can be ascertained, the message begins to take meaning.. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

Jan 1, 1937

The mining fraternity of North America was grieved and shocked to learn of the death of Dr. Willet G. Miller on Feb. 10, 1925. Doctor Miller was for many years the Provincial Geologist of Ontario and the one who more than any other had contributed by his personal work and the reports of his subordinates to the recent extraordinary mineral development of the Province. Doctor Miller was fifty-eight at the time of his decease. A man of unusually stalwart physique, he seemed destined to many years of useful service. His friends in both the American and Canadian Mining Institutes can with difficulty reconcile themselves to his loss. Doctor Miller was born in 1867 in Port Rowan, Ont., on the shores of Lake Erie. After preparation in the high school of his native town, he entered the University of Toronto and took his bachelor's degree in 1890. He pursued graduate studies in geology at Chicago, Harvard, and Heidelberg Universities. In 1893, he was first appointed lecturer and soon thereafter Professor of Geology in Queens University, Kingston, Ont., a chair which he held until 1902. He was then appointed Provincial Geologist of Ontario and was placed at the head of the Survey which was attached to the Department of Mines. Within the next year, 1903, he performed the service that made him famous. In the summer of 1903, in connection with the building of the Ontario Government Railway toward an objective on James Bay, veins had been noticed by construction parties just north of what is Cobalt Lake today, and in the rocky pass that is now traversed by the main line of the Canadian National Railway en route to Vancouver. The pink stain of cobalt bloom on the vein, known later as La Rose, caught the eye of a workman; in November, Doctor Miller recognized the silver in it, and brought the possibilities of the district to general attention. In December, he published an article in the Engineering and Mining Journal, stating that the veins could be worked at a handsome profit. During the winter and spring, the mining interest awoke, which resulted in the astonishingly productive silver district of Cobalt; but in which, Doctor Miller, because a government official, scrupulously refrained from having any financial interest whatever. Seldom has so high a sense of honor been manifested; and as the result, Doctor Miller commanded confidence and respect to an extraordinary degree. Hard on the discoveries at Cobalt came, in the next few years, those at the other famous camps in Northern Ontario; and step by step with them, reports issued from

Jan 1, 1925

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Benny J. Nelson

To obtain information on the effect of gallium upon the corrosion of magnesium alloys, tests were made on the commercial alloy AM52S (Mg-3 pct Al-1 pct Zn-0.2 pct Mn) and experimental

Jan 1, 1957

By Howard Hughes

IN drilling for water and oil to reasonable depths through the generally soft yielding clay and sand formation of the Coastal Plain of Texas, . Louisiana, and Mississippi, the rotating method of drilling was adopted, principally on account of the easy and quick penetration, and the low cost of the drilling plant. In favorable ground, free of heavy gravel and rock strata, as much as 1,000 ft. has been drilled in less than 36 hr., although such performances were of course rare. Hydraulic rotary drilling, or, as it is now called, rotary drilling, was used in the above States as early as 1880. The plant consisted of an ordinary derrick, a 25-h.p. boiler, a small hoist, a steam pump, and a water swivel with hose attachment, and an ordinary flat diamond-pointed bit. The successful drilling in of a phenomenal oil well by this process on Spindletop, near Beaumont, Texas, on Jan. 10, 1901, and the ascertained impracticability of drilling subsequent wells in the same locality by other methods (owing principally to heavy quicksand under pressure from below), brought rotary drilling into great prominence, practically to the exclusion of any other process throughout the Coastal Plain, and later on elsewhere. The method, as its name implies, involves the rotation of a pipe by means of machinery placed on the derrick floor. A drill bit attached to the lower end cuts a clearance for the drill pipe, with much the same motion and effect as an auger. Water forced through the drill pipe by means of a pump, and escaping through the bit, removes the cuttings and returns to the surface outside the drill pipe. In this manner the hole is kept open, permitting the drill stem to rotate freely. The pressure of the column of muddy water holds up the walls of the hole until it has been cased. Practically all the wells of the Gulf coast region, numbering nearly 10,000, have been drilled with this system. During the last five years its use has been extended to many other States and countries.

Jan 3, 1915

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1'2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.' Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962

By P. Marier, T. R. Ingraham

When cylindrical powder compacts of nickelous oxide (NiO) are heated in an equilibrated stream of SO3, SO,, and 02, in the temperature range 500°to 800°c, tlickelous suljate (NiSO4) is formed as an adherent layer on the oxide. The reaction is diffusion-controlled, with an activation energy of 13 ± 3 kcal per mole. When cylindrical powder compacts of NiSO4 are heated in a stream of dry nitrogen in the temperature range 1000 0to 11500C, NiO is formed at a well-defined interface between the sulfate and oxide. The interjhce migrates into the sulfate at a constant rate at a constant temperature and gas flow. The reaction rate increases with increasing gas flow and decreases with increasing partial pressure of SO3 in the gas stream. Resolution of the partial-pressure data with a Lang-itzliir Adsorption Isothern suggests that about 80 pct of the NiO interface is covered with SO3. The heat of adsovption is about 68 kcal per mole. The activation energy of the decomposition process is 61 ± 3 kcal per mole. MOST of the work reported on the formation and decomposition of nickel sulfate is related to thermodynamics.1-3 No quantitative work has been reported on the decomposition process. The only kinetic work reported on the formation is that by Fletcher and shelef.4-6 whose main purpose was to study the effects of alkali metal sulfate additions on increasing the rate of nickel sulfate formation. They found that, in the absence of an additive, only small amounts of sulfate were formed and the kinetic data were difficult to interpret. However, they suggested that the sulfa-tion of nickel oxide is a diffusion-controlled process for which the activation energy is approximately 17 kcal per mole.6 In this paper, both the formation and decomposition reactions will be examined; and based on the effects of temperature, flow rate, interfacial area, and partial-pressure of sulfur trioxide, mechanisms and activation energies will be suggested for both processes. EXPERIMENTAL Material. The nickel source material used in all experiments was Baker and Adamson Reagent Grade NiSO4. 6H2O, for which the following analysis was supplied by the manufacturer: C1, 0.001 pct; NO3, 0.005 pct; Co, 0.02 pct; Cu, 0.005 pct; Pb, 0.002 pct; Fe, 0.001 pct: insol, 0.005 pct. The anhydrous sulfate was prepared by heating the hydrate at 420°C in a muffle furnace for 5 hr. Nickel oxide was prepared by decomposing the sulfate at 950°C over a period of 10 hr. Method. The technique used for measuring the rates of formation and decomposition was developed earlier in these laboratories.7-8 The method is based on the observation that the kinetic parameters of a reaction can be established in a flow system, with specimens prepared by compacting powder to a uniform pellet shape. The results are identical with those established with solid polycrystalline specimens or single

Jan 1, 1967