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By Behram H. Wadia, Robert S. Lehto

A new metallurgical treatment for capturing as much of the values as possible from zinc refinery feed has been devised by personnel in Cerro de Pasco's Peruvian operation at La Oroya. Results from a pilot test illustrate that 50 metric tons of throughput can be maintained whereby substantially all the silver and copper report in the sponge iron while zinc and lead with indium and cadmium volatilize in the fume. This new technique named the Zileret (zinc leach residue treatment) process complements the electrolytic system used in the refinery so that all values in a zinc concentrate are economically recovered. In the system, dried zinc leach residue is pelletized with soluble zinc sulfate which already exists in the leach residue and a finely divided reducing agent such as anthracite coal. Upon heat addition, the loose anthracite in the charge maintains a reducing atmosphere while the free space above the charge has an oxidizing nature. When the charge reaches the reaction zone at about 1100°C, metals such as zinc, lead, cadmium and indium volatilize from the pellets, are oxidized in the upper kiln atmosphere, and are then carried in suspension as an oxide fume to the cooler and baghouse. The copper and silver content in their reduced forms, along with the iron, discharge from the kiln as a calcined product which is then cooled to below 130°C before being exposed to the air.

Jan 9, 1969

By H. P. Willard, R. W. Gates

Basic Inc., has been mining magnesite and brucite for 27 years at Gabbs, Nev. This is a medium sized open-pit mine. The magnesite deposits are in north-western Nye County about 30 miles east of Luning, Nev., on the west slope of the Paradise Range, at an elevation between 5000 and 6000 ft. The magnesite and associated brucite is used to make magnesia refractories employed principally in the steel industry and magnesium oxide for various chemical uses.

Jan 10, 1963

By H. H. Stoek

Mine models have three distinct uses: 1. As exhibits in expositions and museums. 2. As exhibits in law suits. 3. As illustrations in teaching mining engineering. All three uses are in a sense educational. The third, or distinctively teaching function, has not been extensively developed in America as it has been abroad, chiefly because of the cost of the models and the scarcity of model makers. In connection with expositions, such as the Columbian, the Louisiana Purchase, and the Panama-Pacific, a number of very good mine and metallurgical models were prepared with funds furnished by State commissions, by mining organizations or mining companies. At the close of these expositions, some of these models have been deposited in National or State museums or in educational institutions, but too many of them haw been lost, or have been stored away in some mining company's office or in the basement of some State building, where they have been lost sight of and have gradually fallen to pieces. A visitor to a German mining school is impressed by two facts: 1. The mining laboratories are in general inferior to those in America. 2. The mining museums are infinitely superior to ours, particularly in models exhibited. One may reply to this comparison by saying that a museum is necessarily a work of time. From the historical standpoint this is, of course, true, but it is not necessarily true in connection with a working museum intended to illustrate current practice. For instance, the oldest mining school in Germany, that at Freiberg, has much excellent historical material, but very little on modern practice, while Berlin, one of the youngest German mining schools, has a most extensive and valuable collection of modern appliances and models. This is true in spite of the fact that one of the best-known model shops is at Freiberg, from which many of the models to be seen in America have come. Because many of the models in American mining schools have come from

Jan 1, 1918

By D. D. Dunkin

Sandstone has been prepared for glassmaking purposes, and marketed from the White River Valley in Arkansas at Guion, Izard County, since about 1910—soon after the completion of the White River Branch of the Missouri Pacific R. R. Co. Until 1921, operations were somewhat spasmodic and ended in many failures. In that year a plant was built by the Silica Products Co., Inc., and since that time the operation has been continuous and steady. The land is held under leases, covering about 30 square miles of the best sandstone adjacent to the railroad. Most of the product is shipped to glassmakers. Geology The St. Peter sandstone is rather widely distributed in north central Arkansas and is exposed most prominently in outcrops along the slopes of the White River Valley and its tributarirs that form the division between the Boston Mountains to the south and the Salem Plateau of the Ozarks to the north. It is of Ordovician age and is generally underlaid by Cotter dolomite and capped by Plattin limestone, except in the vicinity of Bellefonte and Everton. At those places, it is a massive cross-bedded, laminated, saccharoidal sandstone; underlying it is the Everton limestone and overlying it, the Joachim magnesium limestone The sandstone at Everton contains numerous phosphatic pebbles and inclusions of sandy limestone. The irregularity of cross-section, the evidence of sorting action and the phosphatic pebbles appear to be indications of secondary deposition The St. Peter sandstone occurs as a massive formation in the picturesque bluffs along the White River Valley from near the eastern escarprnent of the uplift northwestmard into the Ozarks. The exposure shows a series of gentle anticlinal and synclinal folds. The greatest thickness is at the southeastern end, where it is over 100 ft. in many places. It thins out to the north and west and then to isolated and scattered deposits which cap the ridges and mountains of the Ozarks.

Jan 1, 1928

By A. U. Seybolt

The solubility of oxygen in a iron has been determined in the range between 700° and 900°C. The solubility is a function of temperature and varies from about 0.008 pct oxygen at 700°C to atureandabout 0.03 pct at 900°C. The heat of solution is approximately +15,500 cal per mol. AS pointed out in a recent paper by Kitchener et al.,1 there has been a lack of agreement among many investigators even as to the order of magnitude of the solid solubility of oxygen in the various forms of iron. This lack of agreement is attributable in large part to the difficulties in the determination of a small oxygen solubility; but because the problem has remained so long unsettled, it also indicates a lack of interest which is rather surprising when the demonstrated importance of small amounts of soluble nonmetallic impurities in iron is considered. The work of Kitchener et al. apparently leaves the solubility of oxygen in iron in a satisfactory state, but no attempt was made to investigate the solubility in a iron. The solubility of oxygen in a iron is actually of greater interest, since it is in this form that iron and mild steels are employed ordinarily. That the effect of oxygen in iron is of more than theoretical interest has been well established by Fast,' and more recently by Rees and Hopkins," who demonstrated that oxygen in the range between 0.0008 and 0.27 wt pct has a pronounced effect upon the mechanical properties. Previous Work and Methods Used To report in detail the literature relating to the solubility of oxygen in a iron would require an inordinate amount of space. For those interested in reviewing this work, a bibliography4-13 of the more significant papers is appended. In general, two methods of studying this problem have been used. One is the gas-metal equilibrium method where the H2O-H2-Fe or the CO2-CO-Fe equilibria have been used. The other is the more direct approach of the oxidation of thin strips of pure iron by packing in mill scale or by air or gaseous oxygen at some desired temperature. In this method oxygen is allowed to oxidize the surface and then to diffuse inward until saturation is obtained. In the gas-metal equilibrium method the oxygen dissolved in solid iron at a given temperature is proportional to the ratio of the water vapor-hydrogen pressures or the CO2-CO pressures over the sample for small ratio values. If the ratio becomes higher than a critical value, then an oxide phase makes its appearance (the solution becomes supersaturated). In principle, it is possible to use a series of H2O/H2 or CO2/CO ratios and to find by analysis the corresponding amounts of oxygen in solid solution at constant temperature. At the point where a very small increase in the gas ratio (increase in oxidizing powder) produces a large increase in oxygen content, the solid solubility limit is reached. Alternately, if the critical ratio is known, it is possible to use the procedure of Kitchener et al.1 and to use a ratio which is near but below the critical one. The solubility corresponding to this lower ratio will not be the saturation solubility at the temperature employed, but the saturation solubility can be calculated by multiplying the measured solubility by the critical ratio over the ratio used. However, in the case where oxygen gas is the oxidizing medium, the saturation solubility is not a function of pressure, providing the pressure exceeds the dissociation pressure of FeO in equilibrium with iron. This is 1.2x10-16 mm at 800 °C, according to Dushman." As pointed out by Darken17 in discussing the FeO phase diagram, most of the possible errors tend to yield high values of oxygen solubility. For example, one circumstance which evidently caused the reporting of many high values was the use of finely divided or powdered iron in the gas equilibrium method. Because of the large surface area of such a sample, and the likelihood of some surface contamination if only by exposure to air, the results tended to be high. The direct oxidation method which was used in this work has the advantage in that it is simple and direct, but it suffers from one disadvantage: equilibrium can only be approached from the low oxygen side. The important factors to be kept under control are the following: 1—use of high purity iron to avoid internal oxidation (oxidation of readily

Jan 1, 1955

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By G. Thodos, W. F. Stevens

The point-source function introduced by Horner' us a solution to the general unsteady-state equation for the flow of fluids through porous media has been utilized to calculate pressure profiles for adjacent wells as a function of time. By trial and error, the time at which the pressure waves meet to cause interference can then be calculated. For this calculation, the time of interference is arbitrarily defined as that time when both pressure waves exhibit a pressure decrease of 25 psi ar the same point within the formation. To illustrate the method, an example involving two adjacent wells producing at different rates has been worked out and is presented in detail. INTRODUCTION The initiation of production of a new well is usually accompanied by pressure drawdown measurements in order to establish the extent and characteristics of the formation. The interpretation of such pressure drawdown data is based on mathematical developments involving a single well in an infinite reservoir. If more than one well is present in a reservoir, the possibility of interaction between wells exists. Therefore, care must be taken in interpreting the pressure drawdown data. It becomes important to be able to determine when this interaction, or interference, becomes significant. This paper presents a method for the prediction of the approximate time of interference between two such adjacent wells. The basic differential equation describing the pressure distribution existing during unsteady-state flow of a slightly compressible fluid has been solved by Hor-ner.' for a constant production rate from a circular homogeneous reservoir of infinite extent. The solution utilizes the point-source function to define the pressure at various points within the formation as a function of time. The resulting expression is: q = production rate, STB/D ,;= formation volume factor, dimension-less µ = fluid viscosity, cp k = formation permeability. md H = formation thickness, ft C - fluid compressibility, psi' F = formation porosity, dimensionless R = distance from centerline of well, ft T = production time, hours Ei(—u) = Ei-function of U Eq. 1 may be used to calculate the pressure profiles generated during production from a single well in an infinite reservoir.

By E. E. Russell Tratman

The use of dynamite in cold weather is attended with some difficulty, owing to the freezing of the material and its consequeut liability to fail to explode when the fuse is fired. With proper methods and care the dynamite can be thawed with reasonable safety, but numerous accidents occur (more than get reported in the public press), due to carelessness in the operation and to the treacherous nature of the material, or a combination of both conditions. Dynamite will stand treatment at one time which at another time will result in explosion. An expert on explosives says that the most dangerous means of thawing cartridges are ingeniously devised by ignorant laborers; baking, boiling and toasting being favorite methods, while at a stone-quarry, in one instance, an apparatus was arranged for steaming the cartridges over a pot of boiling water. In this latter case the nitro-glycerine leaked through the canvas cover and settled on the bottom of the pot, with the result that an explosion occurred, the water acting as a tamping to the charge. The fact that small quantities of explosives containing nitroglycerine will burn quietly and without explosion if ignited by direct contact with a flame, has led to the dangerously mistaken reasoning that merely heating the explosive can produce no ill effect. If . a dynamite cartridge is ignited or placed in a fire it will probably burn harmlessly away, but if placed on a stove or in an oven and

Jan 1, 1893

By Edwin Ludlow

To THE members of the American Institute of Mining and? Metallurgical Engineers who were fortunate enough to be able to attend the Fiftieth Anniversary at Wilkes-Barre, it was brought home that commercial anthracite requires not only expensive mining but that the milling or preparation of it is also a costly operation, requiring very large capital expenditures and high maintenance and labor costs. The great trouble that coal men meet in discussions of coal problems today is the difficulty the average coal user, especially in the East, finds in distinguishing between anthracite and bituminous coals. They are two entirely separate problems and yet the people who are burning coal complain bitterly of the high cost of anthracite and quote the figures furnished in regard to the prices of bituminous coal and feel that the anthracite operators are making an excessive profit, without realizing the enormous difference in the cost of production in the two fields. The great difference that can be marked is that in this year of industrial depression the prices of anthracite have been not only maintained but have increased during the summer, while the price of bituminous coal has been continually dropping since the first of the year, and yet the same law of supply and demand governs both anthracite and bituminous. In order to understand the situation the two problems must be considered from their separate points of view.

Jan 1, 1921

By William C. Buell

As used in connection with open-hearth or other high-temperature operations, "insulation" refers to a multitude of substances, natural or manufactured, that have the one principal property of preventing the flow of heat by conduction to a greater degree than refractories can prevent it, the principal properties of the latter being resistance to temperature and/or chemical action. The term "control" as commonly applied to the mechanization of management functions is inappropriate without qualification, for without some degree of control of every operation we could produce no steel worthy of the name. Although grouped together in this paper, insulation and control in open-hearth furnaces have little, if any, interrelationship, therefore the paper is made up of two distinct parts. INSULATION OF OPEN-HEARTH FURNACES More than ten years ago the writer proposed the insulation of an acid open-hearth furnace system below the charging floor, and it was accomplished, with gratifying results. Possibly that was the first time the insulation of regenerators and slag pockets of any open-hearth furnace was undertaken, but shortly thereafter such insulation became general, and when the six groups of 15D-ton furnaces' were built in 1929-1930, they were completely insulated below the charging floor. While the practice was accepted at least five years ago, it was not well understood, however, as indicated by the following incident which occurred in connection with an installation made in 1929. After the

Jan 1, 1935

By H. C. Rolseth, R. H. Kohler

Jet channeling made its entry into the granite industry in 1955 and quickly gained acceptance as an economical method of quarrying. Developed by the Linde Division of Union Carbide Corp., this method employs a small rocket-jet burner with a high-temperature, high-velocity exhaust flame that causes granite to disintegrate. It can thus make continuous vertical cuts to free large blocks from granite formations. The Thermal Spalling Process The effect of a thermal device on rock depends upon the rock's spallability. In simplest terms, spalling is the decrepitation resulting from differential expansion of rock crystals due to thermally induced stresses.1 the individual rock properties influencing the spalling characteristic are so numerous and their interaction is so complex that it has so far been impossible to predict with accuracy the reaction of any particular rock to a high-temperature source of heat. Perhaps computers will eventually make such predictions possible, but for the present it is necessary to impose the thermal shock conditions on a sample of the rock to establish its spalling characteristics. The properties most favorable to a high degree of spallability are: (1) Large linear thermal expansion at temperatures below 700º C. (2) High thermal diffusivity at temperatures below 400º C. (3) Equigranular interlocking structure with little or no fine-grained clay or mica alteration products. (4) No significant amounts of soft, low-melting, or elastic minerals or materials which yield after thermal decomposition.

Jan 7, 1969

By Edwards Wichers

The purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcorning paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature. Treatment of Platinum Ore As is well known, the principal source of the platinum metals is a mixture of several native alloys of the metals, found chiefly in naturally concentrated deposits in stream beds or alluvial material. Without attempting to enumerate all of the minerals present, it may be said that the concentrated ore from such sources contains all of the six platinum

Jan 1, 1928

By Kidd, Robert L.

INASMUCH as galena and sphalerite flotation concentrates are being produced that contain over 95 per cent galena or sphalerite, it is not unreasonable to believe that a flotation concentrate assaying at least 80 per cent of native gold can he secured provided the gold is free. As yet, little if any fundamental information has been published concerning the flotation of free gold either alone or in the presence of sulfides. So far, we are unable to make as complete a separation of gold from sulfide minerals by flotation as is possible in, the separation of one sulfide from another by this method. An introductory study of the flotation of several free gold ores has been made in our Utah laboratories. For this study three general types of gold ores were chosen, namely: (1) Quartzite containing 0.26 oz. gold per ton in which no base metals are present; (2) sulfide ore (2.04 oz. Au; 1.31 oz. AO containing pyrite as the only sulfide present and the gold free; and (3) oxidized ore (1.10 oz. Au; 0.70 oz. Ag) from an oxidized zone of the vein from which sulfide ore (No. 2) was taken; little sulfide iron was present.

Jan 1, 1932

By H. O. Hofman

Lime-roasting is a term proposed by Ingalls' for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse un-decomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale,—the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent. of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1908

By Milton E. Wadsworth, T. D. Chatwin

Bulk density variations can usually be minimized by properly mixing the material before moisture measurement. The measuring of moisture on material being with- drawn directly from storage bins requires some form of bulk density correction. In Bethlehem's pellet plants continuous automatic bulk density correction and uniform feed-rate control are obtained with Bethlehem's patented Bin Level Control System. With this sys- tem a single probe, suspended or inserted in the bin, senses whether material is at the proper level in the bin and automatically regulates filter speed to control the filter-cake discharge rate to maintain this level. The level of concentrate in the filter-cake bin can thereby be controlled to within ± 1/2 in. of the point of contact between the concentrate and the probe. Material thickness on the conveyor does not have to be controlled accurately and mix compositions can vary widely as long as they do not contain variable amounts of water-soluble electrolytes. In sinter plants, errors caused by changes in normal feed rate and bed height are minimized by counter-weights that permit the free-floating to maintain a uniform contact pressure on the mix. Large changes in mix resistance can be taken care of either by resetting the control point or by adjusting the calibration control.

Jan 9, 1968

By Robert Pack

INTRODUCTION SOONER or later in the development of any natural resource it becomes highly desirable to know the quantity of this resource in the country as a whole, as well as of the part that is being developed, for the general course and. conduct of the development work must be governed to some extent by the total supply available. An accurate estimate of the quantity of any natural resource is difficult to make; yet if one is diligent enough one can obtain a pretty accurate idea of the quantity of marketable timber, the acreage of tillable land, or the horsepower that may be developed from the streams, for these are things that may be measured. But any attempt to estimate the quantity of some mineral in the ground appears to enter the realm of imagination and it seems that the estimate can be nothing more than a blind guess. It may appear to be especially futile to attempt to determine the quantity of oil and gas that is available in the ground, for these minerals are so vagrant that even if the quantity now available should be known quite exactly, the quantity that will eventually be obtained may be much less, for certain losses in the extraction of both oil and gas are unavoidable, and just what these losses will be cannot be predicted. Though necessarily inaccurate, estimates of such mineral reserves are, however, of distinct value, for they summarize the existing knowledge of the deposits of the mineral and thus enable those who are interested in some industry that depends in one way or another on this mineral to formulate a rational commercial policy. Some time ago, when the price of gasoline suddenly rose in a rather spectacular manner, the writer was one of the U. S. Geological Survey geologists called upon to help to estimate the quantity of oil that could be obtained in the United States, for the fear had become widespread that perhaps the rate of increase in the price of gasoline was a measure of the rate of depletion of the supply of petroleum. It thus became his

Jan 8, 1917

By A. Boltax

The effect of cold work on the electrical and magnetic properties of solution-treated and aged Cu-Fe alloys was studied. The electrical resistivity of solution-treated and of aged Cu-1.7 wt pct Fe samples increased by up to 25 and 140 pct, respectively, follozcing a 55 pct reduction of area. The principle contributions to the increase of resistivity of the solution-treated and aged samfiles are examined. Measurements of the .saturation induction, coercive force, and stacking fault Probability are also reported. 1 HIS paper is the second in a series which examine the behavior of the electrical and magnetic prop- erties of Cu-Fe alloys. The first paper1 was primarily concerned with the effects of thermal treatment whereas the present paper examines the effects of cold work on solution-treated and aged Cu-Fe alloys. The effects of cold work on the transformation of the coherent fcc iron precipitate to the ferromagnetic form2 and the coercive force and remanence3 have already been described, but the unusually large increases in resistivity (up to 220 pct) which occlir with cold work have not been reported previously. EXPERIMENTAL METHOD The methods used for alloy preparation, heat treatment, and electrical and magnetic measurements are described elsewhere.1 The specimens, initially 4-in. lengths of 0.0625-in. diam wire, were cold worked by swaging in hardened steel dies. Following each reduction, the samples were etched lightly in hydrochloric acid to remove surface con-

Jan 1, 1962

William Metcalf, Pittsburg, Pa. (communication to the Secretary*): I am greatly pleased that some one has at last reached what I have long regarded as the only rational explanation yet given of the reasons why steel hardens. Mr. Field claims originality; and doubtless he is entitled to it, but not to priority, mhich must be granted to Prof. John W. Langley.' The difference between them is that Langley says " Tension, probably molecular," and Field says " Tension, probably atomic "; in either case the vital thing after solution is tension. Mr. Field's argument carries with it the idea of increase of density with hardness; if he mill study the facts farther he will observe that the case is just the reverse; that is, the greater the hardness the less the specific gravity; it was just this fact that led Langley to his conclusion, in mhich I have always concurred. Field agrees with Langley that the first requisite for perfect hardening is complete solution of the carbon, not combination; and all of the facts agree with this conclusion. The fact that increase of hardness causes reduction of density was first brought to my notice some 40 years ago, when Major William Wade was testing Jones & Laughlin's cold-rolled iron, and I mas his assistant. We found the well-known increase of tenacity, compressive strength, torsional resistance, and hardness. Specific-gravity tests showed that the cold-rolled iron was less dense than the hot-rolled bars. Major Wade was so surprised at this result that he gave me a lot of samples to weigh, saying that he was not satisfied with

Jan 1, 1904

By J. I. Paige, T. T. Campbell, A. W. Henderson, H. M. Harris

The chlorination of ilmenite concentrates and slags to produce Tic14 suitable for pigment or metal production was investigated by the Bureau of Mines along with the dechlorination of byproduct iron chloride to produce chlorine for recycle and iron oxide., Ilmenite concentrates or slag powders were fed into the bottom of a fluidized coke bed at 1,050º C using chlorine flow rates up to 20 l/min in a 10.2-cm-dim reactor. Tests showed that >95 percent of the various ilmenite concentrates reacted at optimum conditions, and recovery of TiC14 ranged from 95 to 100 percent of stoichiometric. Impurity dusts were removed from the vapors by cyclones and a fiberglass cloth filter. Iron chloride was condensed as a powder with less than 0.4 percent insoluble material. The TiC14 was collected in refrigerated condensers. Iron chloride was dechlorinated at 500º to 550º C by reaction with oxygen in a 16.5-cm-dim reactor using a fluidized bed of Fe2O3. Optimum processing was attained with a FeC13 feed containing 25 wt-pct Fe203 granules treated with 2 wt-pct NaCl catalyst; Under the above conditions, off gas chlorine concentrations of 62 to 90 wt-pct were obtained. During 2- and 3-day tests with technical-grade FeC13, conversion of FeC13 was 94 to 97 percent, chlorine concentrations were 76 to 90 wt-pct, and up to 92 pct of the stoichio- metric Fe203 was removed in the primary reactor discharge. Chlorine

Jan 1, 1976

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,' or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967