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By H. Kosmider, P. Coheur

New processes of blowing with an oxygen-enriched air or gas mixtures of oxygen and steam allow the steelmaker to produce, in a basic converter, a rimmed steel low in nitrogen (0.0020 pct), phosphorous (0.020 pct), and sulphur (0.020 pct). The physical properties (ductility) of the new steels are excellent. Furthermore, from the point of view of economy, these new methods of blowing offer outstanding possibilities. THE natural occurrence of geological deposits of iron ore and local economic circumstances led European blast furnace men to work large quantities of lean iron ore with a phosphorus content as high as 0.5 pct. The iron obtained from these ores generally contains 1.5 to 2.1 pct phosphorus, 3.6 to 3.9 pct carbon, 0.3 to 0.6 pct silicon, 0.04 to 0.08 pct sulphur, and 0.3 to 1.2 pct manganese. To produce steel from this pig iron, the steelmaker has at his disposal several processes. One of the simplest and most economical is the pneumatic process developed by S. G. Thomas in 1879. This process of steelmaking, called the Thomas process, consists of blowing through the bottom of a basic bessemer converter and is used widely in Western Europe, as shown in Table I. Due to the development of tonnage oxygen plants, this process has become more important because the use of oxygen offers new possibilities of steel manufacture. Not only may the quality of the steel be improved, but liquid pig iron also may be used, the composition of which does not meet the heat requirements of the blow with atmospheric air. It is not intended to present here a detailed scientific discussion of the basic bessemer process but rather to discuss briefly its industrial possibilities in the case of rimmed steel and when blowing with atmospheric air, oxygen-enriched air, or gas mixtures of oxygen and steam. This paper is based on the current practice at Klockner-Hüttenwerk Haspe's steel division, and at six Belgian and Luxemburg steel works. The latter are members of the Liege section of the C.N.R.M. (National Institute for Metallurgical Research) and are: ARBED, John Cocker-ill, Esperance-Longdoz, HADIR, Miniere et Metal-lurgique de Rodange, and Ougree-Marihaye, most of which are working with tonnage oxygen plants.' In order to avoid any misunderstanding, it should be noted that most of the techniques to be men- tioned, or similar ones, are used currently at many steel plants in Western Europe. Background The basic converters used in Europe have a capacity of 17 to 65 tons of steel, and are similar in shape to the one in Fig. 1. The lining is brick or rammed dolomite and has a life of 250 to 500 blows. The bottom is rammed dolomite and has a life of 40 to 80 blows. As far as we know, the type of blast used does not appear to have any influence on the life of the lining. Bottom life, on the contrary, depends very much upon the composition of the blast. It is only when

Jan 1, 1955

By Herbert Kilburn Scott

The information in this paper was collected by the author during a five years' residence in the State of Minas Geraes. Outside the State itself, very little is known of the gold-field. Such accounts as have been published are antiquated and contained in publications mostly out of print. The increased attention now attracted to the natural resources of Brazil, and the probability that American capital will be, in the near future, largely invested there, will make an up-to-date account specially useful at this time. I. Historical and General. Soon after the Jesuits founded what is to-day the city of S?o Paulo, gold was discovered in the streams of the neighborhood; and this incited the natives, known as paulistas, to look for it farther afield. After many expeditions into the interior, gold was found in quantity in placer-deposits in the vicinity of Ouro Preto, in 1699, by a prospecting party headed by Antonio Dias. The name of Ouro Preto (black gold) was given because of the superficial dark coating of the gold, and the inhabitants of the district were known as mineiros (miners). Later on, the placers of Cuiaba, in the State of Matto Grosso, were discovered in 1718, and those of the State of Goyaz in 1724. All this territory was at the time a private colony, but on account of its increasing importance it was taken over by the Crown, and in 1739 a royal governor was appointed, with his nominal capital in S?o Paulo, though for a number of years the real capital was Ouro Preto. In 1711 Ouro Preto was raised to the rank of a city, with the name of Villa Rica de Ouro Preto (" rich city of black gold"); and in 1720, by reason of administrative difficulties, Minas Geraes was constituted a separate colony from S?o Paulo, with Villa Rica as its capital. The site of this city

Jan 1, 1903

By Dol Duwez, R. H. Willens

A technique is described by which metastable alloy phases can be obtained by very rapid cooling from the liquid state. The results obtained so far have lead to; 1) extension of solubility limits beyond their equilibrium values, 2) new phases not found under equilibrium conditions, and 3) amorphous alloys. MANY new nonequilibrium phases have been found in alloys rapidly cooled from the liquid state. The technique used in these investigations essentially consisted of propelling a small molten globule of an alloy against the inside surface of a rotating copper cylinder. Since these original experiments were performed, the technique has been greatly improved. The purpose of this paper is to describe in detail, for the first time, a simple and efficient apparatus for producing foils of alloys which are rapidly cooled from the melt and to summarize some of the observations made on these alloys. I) FAST COOLING APPARATUS In the original fast cooling apparatus used by Duwez, Willens, and Klement,' the alloy was melted in a graphite container having the shape shown schematically in Fig. 1. A shock tube was attached to one end of the graphite part to supply the pressure for ejecting the molten globule. The globule was received on the inside of a rotating cylinder located about 0.5 in. from the exit of the graphite container. The globule trajectory made an angle of about 15 to 25 deg with the tangent to the cylinder at the point of

Jan 1, 1963

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of SO2 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 3/4 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no SO2 could be detected in the gases. In all cases the depth of bed was 4 1/2 in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which SO2 determinations were made could not be measured, but has been calculated from the SO2 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on SO2 concentration in sintering under ordinary conditions show a high SO2 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum SO2 concentration is obtained 2 ½ min. after

Jan 1, 1942

By F. P. Dewey

At the Wilkes-Barre Meeting of the Institute, Dr. J. Lawrence Smith, in the course of his remarks on some peculiarities in the composition of irons, alluded to the so-called " bucltshot" iron, and exhibited a specimen of this material. He said that when the small granules, or shot, were separatetl from the mass, they could be flattencd under the hammer, and inferred that these particles had been decarburized by the blast before sinking into the hearth of the furnace, and thus we had the exceptional production of wrought iron in the blast furnace. I have recently obtained a characteristic specimen of this variety of iron from one of the furnaces at Orbisona, Pa. Considerable uncertainty existed as to its true nature and the conditions of its production. Its weight seemed to preclude the idea that it containetl much or any slag, yet its lack of strength indicated that it was not homogeneous cast iron. At times considerable quantities had been produced, which could only be utilized by charging in the furnace and remelting. The specimen, on the freshly fractured surfacc, appeared to consist of flattened globules of iron cemented together by a bluish material which one would naturally suppose to be slag, and qualitative examination for lime strengthened this supposition. It was quite difficult to obtain drillings, as there was a tendency to split in several directions as soon as pressure mas applied; but enough was obtained to undertaltc quantitative determinations. They were found to consist of two portions—one attracted by the magnet, and the other not. By repeated separation the magnetic portion was found to be 94.44 per cent., and the non-magnetic 5.56 per cent. Analyses of these gave the following results: Magnetic Portion. Non-magnetic Portion. Percent, Percent. Graphite,.....3.480 Lime,. . 71.41 0 = 24.028 Combined carbon,. .. 0.260 Magnesia,. trace. Silicon,..... 2.790 Protox. of Phosphorus,.... 0.412 iron,. trace. Sulphur,.....0.292 Sulphide of Copper,.....0.110 caleium, 3.67 S= 1.72 0 = 3.440 Manganese,.... 0.500 -Iron (by dif.).,. .. . 91.206 27.468 --Silica,. 24 62 0 = 13.131 100.000 99.90

Jan 1, 1879

By E. P. Klier, Volker Weiss, George Sachs

IT has been shown that the isothermal transformation of austenite in a special steel can be modified by isothermal holding in the high subcritical transformation range.' Since this treatment potentially leads to increased hardenability, limited testing has been completed to determine if the stabilization effects observed with this treatment can be used to advantage in the heat-treating of 4340 steel. As an index of the effects of the several austenitizing treatments on the hardenability of the steel, Jominy-type hardenability tests were completed for specimens 2.5 in. in diameter and 8 in. long. Since the steel studied is to be used at strength levels where notch sensitivity is of major concern, notch sensitivity after selected austenitizing treatments has been evaluated by notch tensile tests for several specimen sizes. The steel composition and the austenitizing treatments are given in Table I. The test specimens are presented in Fig. 1. The hardenability data are given in Fig. 2 and the notch tensile properties are presented in Fig. 3. The hardenability of the steel investigated when determined by use of the standard Jominy test specimen2 as high and remained essentially unchanged for the different austenitizing treatments. For the larger test specimen, as has been shown by other investigations," the characteristic hardenability indexes are changed and it becomes possible to isolate austenitizing treatments which promote maximum hardenability. The stepped austenitizing treatment promotes higher hardenability as is indicated in Fig. 2. The evaluation of notch sensitivity for very high strength steels is best accomplished by means of the notch tensile test. The experimental conditions of the test, however, modify the notch strengths measured, and in the present experimentation an effort was made to achieve a limiting notch condition by fixing the notch root radius at 0.001 in. while the specimen diameter was allowed to increase from 0.3 to 1.1 in.* For this root radius the notch strength, 0.3-in.-diam specimen, and this trend differs from that for the larger specimens. At the highest tempering temperatures the 1.1-ip.-diam specimens yield comparable results for the austenitizing treatments compared. However, as the tempering temperature is progressively lowered below 800°F, em-

Jan 1, 1958

By Jasper L. Stuckey

PYROPHYLLITE, first identified as soapstone,1 later as agalmatolite,2 and finally as pyrophyllite,3 has been known to occur in North Carolina for more than 130 years and has been produced intermittently in commercial amounts for the past 100 years. Pyrophyllite mining, however, has become a major industry in North Carolina only during the past 25 years. North Carolina and California are the chief producing states. Current annual production averages 125,000 tons, of which slightly more than 90 pct comes from North Carolina. Distribution and Geologic Setting: All known pyrophyllite deposits in North Carolina are associated with rocks of the Carolina Slate Belt,4 which is composed of a vast series of metamorphosed volcanic and sedimentary materials, occurring as two zones extending in a northeast-southwest direction across the state. The larger of these zones, lying in the central Piedmont region, varies from 8 to 50 miles wide. The smaller zone lies along the eastern edge of the Piedmont region and is partly covered by coastal plain sediments.

Jan 1, 1958

By W. C. Lacy

This article is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The author feels that, although there does not appear to be any one technique or characteristics that will suffice as an index to the determination of stable slope angles, a combination of seismic methods as outlined here, detailed geological mapping and logging of core, and a better understanding of the angle of internal friction in rock types will permit accurate estimation. A mining engineer friend once remarked, "If we don't have pit slope failures, the slopes are too flat." Since economic justification of an open pit project is based upon ultimate pit slopes, we cannot wait until the pit is developed and slopes established by trial and error. Some combination of geological and/or geophysical techniques must be developed to permit accurate prediction of stable slope angles and to suggest modification of pit outlines to result in slopes enabling maximum economic yield. This presentation is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The principle of the weakest link applies to any slope stability evaluation and necessitates detailed geological examination and recording of observations. Physical failure will occur along any surface where shearing stress exceeds shearing resistance. Rock conditions are seldom uniform even within a single cut or pit face, so stability conditions will vary. Consequently, both plan outline and ultimate slope limits must be tailored to the specific situation. Economic advantages to be gained by slight increases in slope angles in deep pits are well recognized and stimulate efforts to obtain maximum permissible slope angles. MECHANICS OF SLOPE FAILURE Excellent reviews on the nature of slope failure have been presented+2,6,8,11 For the purpose of this study, the writer considers failure to take place by one or more of three processes: 1) ravelling, 2) translation or slope failure, and 3) rotation or base failure (Fig. 1). The effects of increased pore water pressure in soils were recognized in 1923 by Terzaghi in his development of the concept of effective stress, and he has applied the same principle to jointed rocks designating water pressure as cleft-water pressure.8 Cleft-water pressure in a rock slope reduces normal pressure on the plane of failure, thus reducing shearing resistance and resulting in slope failure. In the following discussion it is assumed that adequate drainage is supplied to prevent any build-up of water pressure. This is the first step in any program to establish maximum slopes. Ravelling: Ravelling occurs in rocks with low cohesion and entails the free movement of individual fragments ranging from single rock falls to running ground. Removal of lateral support wherever slope angle exceeds the angle of repose of the rock parti-

Jan 1, 1963

By C. E. McManus

MANY mechanical advances have been made on mining equipment during the year 1951. There have been a number of trends established and many modifications made on open-pit equipment to increase the efficiency and availability of all the machines necessary in the moving of overburden and iron ore. Some years ago, the trend toward larger shovels for the loading of off-highway trucks began, but in the last year, it has become general practice to use the 5 to 7 ¼ -yd quarry-type shovels in the loading of haulage units. For years these larger shovels were used in the locomotive haulage pits. As the truck capacities increased from 15 to 20 to 30 tons, the need for larger loading units became apparent. Today in most mines, large shovels are in evidence and a few 8-yd shovels will be delivered this year for loading off-highway trucks. Torque Converter-Shovel The Diesel-driven shovel with its friction bands has been modernized with the torque converter. There have been about ten shovels remodeled to take a torque converter in the drive system. The large high-torque, low-speed Diesel engine was removed and replaced by a high-horsepower, high-speed, automotive-type engine. This engine was connected directly to the torque converter. The torque converter was connected to the shovel through the standard original sprocket and chain. Dual governors controlled engine performance. One governor controlled the high idle of the engine; the other governor, which is connected through a flexible shaft to the output shaft of the converter, controlled the loading of the engine. With this dual governor hook-up, the engine anticipates load conditions and is operating at high idle and full throttle before the shovel load is transmitted back through the converter to the flywheel. It has been found that with this automotive-type engine and converter, the shovel capacity has been increased about 20 pct. Also, the wear on the friction bands, breakage of hoist cables, and other mechanical breakages has been reduced materially. Alloy-Steel in Shovels The shovel equipment manufacturers have been experimenting with low-temperature-strength, high-alloy steels to combat the excessive breakage that occurs in extremely cold weather. High-nickel alloy steel has been used in critical areas that are affected by low temperatures, the most notable being dipper sticks. Most shovels ordered today are equipped with some of this special, alloy steel. More and more manganese alloy is being used for replacement parts such as shovel pads, idlers, drive sprockets, etc. Although the initial cost of these parts is considerably higher than the standard replacement items, the life of these manganese parts is considerably longer and well worth the added expenditure. Dipper-teeth repair is still a problem. Most companies use the small replaceable inserted tooth. It has become common practice among some of the companies to "job out" their dipper-tooth repairs to outside welding companies. This necessitates an additional inventory of teeth, but it does guarantee an adequate supply of replacement teeth at all times. These contractors have set up their shops on a production basis and can do an acceptable job at a high rate of speed. Thermite welding has been used in retipping teeth. To date, the process cannot be called successful but with improvements the time required to repoint the dipper teeth will be decreased considerably. The submerged arc process has been tried in the replacement of these dipper points, but like thermite welding has not proven successful. Here again, if a method can be developed to use submerged arc, the job of teeth repair will be made much easier. New model shovels in 6 ½ and 8 cu yd sizes fea-

Jan 1, 1952

By M. R. Hatfield, F. J. Vosburgh

IN a recent article,† it was shown that in the blast furnaces in Germany that are lined with carbon blocks no cooling plates are used, and that shower cooling is employed on the hearth and bosh sections. While one of the authors was in Germany he was told that one furnace was being operated without even the shower cooling on the bosh section, though the hearth section was shower-cooled. In discussion of this interesting situation with a number of blast-furnace operators in this country, it was made clearly and promptly evident that shower cooling was very unpopular, probably because of its messiness and its ineffectiveness. Both of the causes for the dislike of shower coolings are reasonable ones. Shower cooling can be and frequently is messy, but the present cooling of blast furnaces leaves much to be desired on that score. Shower cooling is ineffective as compared with plate cooling, so far as its usefulness in keeping the bricks cool enough not to melt or fall to pieces is concerned. However, the introduction of carbon linings changes the situation. No one is concerned with keeping a carbon lining cool, for no temperature in the blast furnace has any effect on carbon, which is just as stable at 3000°F. as it is at 70°F. The only concern is for the shell-to keep it cool enough for safety and comfort and for that shower cooling is sufficient. Of course, with only the shell to cool, instead of the shell plus all the refractory material, much less water would be required, and the necessity for constant attention to the flow would be lessened, as the hundreds of inlets and outlets would be eliminated. Probably half of the water used in cooling a blast furnace is used for cooling the shaft and tuyeres and the remainder for the bosh and hearth sections. However, in view of the dislike of shower cooling in the United States, and particularly because at least one German blast furnace is operated with no cooling of the bosh section, thought was given to the possibility that a carbon-lined blast furnace might be operated without any cooling of the entire carbon-lined portion. For that reason a series of experiments was performed to determine what might be the temperature of the shell of a blast furnace protected by a carbon lining and operated under varying conditions up to a maximum inside temperature of 3000°F. EXPERIMENTAL PROCEDURE A schematic diagram of the experimental setup is shown in Fig. I and a photograph of the entire assembly in Fig. 2. The heating element was a carbon tube nominally 2 5/8 in. o.d. by 2 in. i.d. by 30 in., used as a resistor. Power was furnished by a 15-kva. transformer operating

Jan 1, 1941

By G. Reinberg, C. D. Clarke

Most underground mining operations are dependent on pumping installations to keep the mine unwatered. The reliability of such installations is obviously of paramount importance. The volume of water to be handled is often considerable, and the total head is relatively high. In these cases, both capital cost and operating expense of the pumping installations will become significant factors in overall mining costs. To insure reliability and to keep efficiencies, and hence operating costs, within acceptable limits it goes without saying that mechanical maintenance of a mine pumping installation must receive scrupulous attention at all times. Large mine pumping installations today almost invariably use multistage centrifugal pumps, since positive-displacement units would not be economically competitive except under very unusual conditions of small volume combined with extremely high heads. Centrifugal pump maintenance, under ideal circumstances, would be confined to parts subject to normal running water, i.e., bearing surfaces, stuffing box packing, and shaft sleeves. Under adverse conditions, however, metal may be lost from the wetted surfaces of a pump by erosive or corrosive action of the pumped fluid, and maintenance costs can easily attain enormous proportions.

Aug 1, 1956

By John D. Morgan, Sylvain J. Pirson

An instantaneous and continuous analysis of a mineral suspension should be of great value in controlling various mineral preparation processes. Described herein is a method of analysis based on the use of high-frequency alternating current, which, under certain restrictive conditions, could be of use. Theoretical Considerations In a suspension of conductive minerals, the electrical effect primarily responsible for the variations in electric conductivity is the capacitance. In Fig Ia, let an alternating voltage E be applied across two electrodes F and F', between which are two rows (S and T) of mineral particles, all of approximately the same size, immersed in a fluid. Let the number of rows of particles between the electrodes be R and the number of particles in each row be N. If A is the area of a particle, D is the distance separating two particles, and k is a constant depending on the fluid, the capacity, CO, of the particle system will be given by: KRA C°= ND Referring now to Fig Ib, let R, the number of rows, be held constant, but let N, the number of particles in each row (S and T), be increased X-fold. The capacity, C1, of

Jan 1, 1949

By W. F. Rochow, W. C. Burke

Numerous designs of linings and accessories, including dams, lifters, and heat exchangers, contribute greatly to kiln efficiencies. Greater conductivity is achieved with basic brick than with fireclay and high-alumina refractories, depending largely upon the use of steel plates in radial joints between adjacent brick to increase heat transfer through the lining. Refractory lifters expose all portions of the load to radiant or convective heat and raise some portions to higher temperatures by cascading the load down through the path of the hot gases.

Jan 3, 1955

By H. E. Biber

DURING the production of tin plate a thin layer of FeSn2, is formed at the interface between the steel sheet and the protective tin coating. Because excessive amounts of this alloy layer are undesirable, the kinetics of its formation is a subject of interest in the tin-plate industry. A recent study of this subject at our laboratory uncovered a relationship which should be of general interest to anyone studying kinetics of reactions in metallic systems. It had been previously concluded that, at any given temperature in the range 175" to 330°C, the Fe-Sn alloy layer would have a parabolic growth rate.1,2 However, our studies showed that this rule apparently holds only when the tin plate is heated very slowly to the "reaction" temperature; when the tin plate is rapidly heated, considerably different growth rates occur. An example of this effect of heating rate on growth behavior is contained in the accompanying results of alloy-layer growth measurements at 240°C in oil baths stirred at 10,500, 1800, and 0 rpm. The heating curves for these three conditions are given in Fig. 1, and the growth data are presented in Fig. 2. With the rapid heating rate, provided by the stirring at 10,500 rpm, the alloy layer had three distinct stages of growth. In the initial stage, which persisted well beyond the time required to heat the tin plate to bath temperature, the alloy layer formed very rapidly. The growth followed a rate law of the form w = ktn where n > 1. This initial stage was followed by a growth-retardation stage of about 50-sec duration in which little additional alloy was formed. In the third stage the growth again followed a rate law of the form w = ktn, but here « =0.3. With the intermediate heating rate provided by stirring at 1800 rpm, the three-stage nature was less pronounced and the slope of the third stage increased (i.e., n > 0.3). With the slow heating rate provided by the unstirred oil bath, the alloy layer grew in two stages. The initial rapid-growth stage persisted only until the specimen was heated to bath temperature, no growth retardation was observed, and the slope of the main portion of the plotted data was greater than in the stirred baths, having a value of almost 0.5. Similar results were obtained for other bath temperatures in the range 200" to 300°C. This effect of heating rate on growth behavior may be due to changes in the rate of nucleation of FeSn, crystallites. The iron and tin are in contact from the onset of heating. Thus the initial formation of FeSn, occurs not at the "reaction" temperature but rather while the tin plate is being heated to that temperature. Because nucleation is in general temperature-dependent, different heating rates could cause different over-all nucleation rates, which in turn could cause different growth behaviors. A more detailed discussion of the growth of Fe-Sn alloy layer and the effect of heating rate will be published shortly.

Jan 1, 1965

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By C. J. Beevers

Tlze influence of zirconium hydride precipitate mprphology on the fructure of Zr-H alloys tested at strain rates of 10- sec at 20° and - 196°C and at strain rates of -500 sec.-1 at 20°C has been inves-tigated. The critical stage in the embrittlement of these alloys was the fracture of the zirconium hyhide precipitates to form large interval cracks at a stress of 25,000 10 137,000 psi. In specimens con-temping up to 100 ppm H the preciptates existed as isolafed platelets in the zirconium matrix and their fracture as enhanced by low temperature (—196°C) and high strain rate (-500 set-f) loading. These resl~lts lead to the conclusion that the rate of strain hardening of the zirconium metal controls the frac-tzrm of the hydride platelets. Increased hydrogen contents of 500 to 2000 ppm resulted in an increase in the 1)volume fraction and size of precipitates and crlso led to crack propogation in the hydride at both 20 and —196C at the low strain rates (10'* sec-'). Quenching led to refinerment of hydride precipitate size and reduced the degree of embrittlement at — 196°C; this effect is attributed to the absence of fracture of the fine precipitates. The formation of zirconium hydride precipitates has been shown to be the cause of hydrogen embrittlement of zirconium.' Several investigators'-" have studied the problem in broad outline, demonstrating that impact-loading conditions, testing temperatures below room temperature, and increasing hydrogen content produce increased brittleness. For example, Muehlenkamp and schwope2 showed that the transition temperature for notched impact tests was raised from 150" to 350°C on increasing the hydrogen content from 45 to 490 ppm. The degree of embrittlement is also controlled by the morphology of the zirconium hydride precipitates. The solubility of hydrogen in zirconium decreases from 600 ppm at 550°C to 10 ppm at 20"C,~ so that the form of the zirconium hydride precipitates (ZrH2) can be modified by varying the cooling rate through the Zr-aZr + ZrH2 phase boundary.= Forscher showed that quenching a specimen containing 35 ppm H from above 315°C resulted in a reduction in area of 70 pct at -196"C, whereas slowly cooling from above 315°C resulted in a ductility of half this value. The role of the hydride precipitate in the fracture process has been examined by Young and schwartz6 and more recently by westlake.' From metallo-graphic observations on slowly cooled Zr-H alloys they have suggested that cracks are nucleated in the hydride precipitates by the interactions of twins in the zirconium metal with the hydride. The experiments reported in this paper show that crack propagation in the zirconium hydride precipitates is the critical stage in the embrittlement of Zr-H alloys. The factors influencing fracture of the hydride precipitates and crack propagation in the zirconium metal will be related to the problem of embrittlement. EXPERIMENTAL TECHNIQUES The zirconium used in these experiments was produced from an ingot of vacuum arc-melted iodide zirconium forged down to 1 in. diameter at 800' to 850°C. The 1-in.-diameter bar was surface-machined and cold-swaged to 0.375 in. diameter. After a vacuum anneal at 800°C for 1 hr the hardness was 60 to 70 Vdh. The total impurity content was approxi-

Jan 1, 1965

By Earl L. H. Sackett

Barite, although not a glamour mineral and probably little known to many of those in the mining business, is produced in the US. in very respectable quantities and is an important factor in the mineral economy of this country. The scope of the various uses of this mineral is perhaps one of the most misunderstood things about it, for it is surprising how many of those with a casual knowledge of the subject speak of its primary utilization in terms of paint pigments and barium chemicals. The life blood of barite utilization, however, is the petroleum industry by virtue of its dependence on this high specific gravity, inert mineral as the weighting material in its drilling fluids. From 80 to 85% of barite usage in the U. S. is accounted for in this manner-in fact, its role in oil well drilling is the only excuse for some of the large-scale barite production facilities which have been developed. Other uses are important and widely varied, but comparatively they are of small scale. They include fine crushed barite of low iron content as a component in glass manufacture, barite as a source material for manufacture of barium chemicals, finely divided barite as a component of some rubbers and ground, bleached barite in pigments. The formerly substantial use of barite in lithopone, however, has declined markedly because of replacement of lithopone by titanium pigments

Jan 5, 1962

By Grover J. Holt

IN order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.o.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the "straight wash" ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces-namely, low price of product and minimum amount of fines-iron-ore concentration has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. [ ] Table I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1943

ALABAMA America.-Foreman, J. T. Ashland.-Sturdevant, J, C. Altalla; Henderson, R. M. Bessemer.-Ball, E. M. Maschmeyer, W. L. McKenzie, W. C., Jr. Birmingham.-Abbott, C, E. Aldrich, T. H. Aldrich, T. H., Jr. Aufderhaar, H. C. Berg, H. A. Blair, C. S. Bush, M. W. Clark. G. H.

Jan 1, 1929