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By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By L. R. Page, J. J. Norton

EFFECTIVE methods for determining grade and reserves of pegmatites in advance of mining have been developed in recent years. When intensive work began on the economic geology of pegmatites during the early years of World War 11, it was widely believed that grade and reserves could be estimated only in a most general way. The literature indicated that not all pegmatite deposits are unpredictable, but statements emphasizing unpredictability and irregularity seem to have been more widely accepted. Many standard references reflect the prevailing opinion that minerals: are unsystematic in their occurrence in pegmatites. Pegmatites have been described as "notorious for their irregular structure," and minerals within pegmatites as "irregularly distributed." "irregularly disseminated," of "erratic occurrence," "proverbially erratic in distribution," "characterized by extreme irregularity in ... size and distribution of the essential minerals, and variety and proportion of the accessory minerals," and "spotty.'"" Over many years, however, geologic techniques have been applied with increasing success to economic analysis of pegmatites. Investigations, chiefly since 1939, have shown that mineral distribution and structure of pegmatites are largely systematic and that detailed geologic study can be used to predict the size and shape of mineral deposits in pegmatites. Because the writers are most familiar with the pegmatites of the Black Hills, S. D., examples cited are from that area." Pegmatites mined in other dis- * All examples are described more cornpletely elsewhere.: tricts are similar to those in the Black Hills," and the techniques described here have been applied by geologists and engineers working in other districts. In actual practice few pegmatite mine operators attempt to make accurate estimates of grade and reserves in advance of mining. Many deposits are too small for mining except on a very small scale; few pegmatite mines have more than ten employes. Hence there is little systematic preparation for mining, and the capital outlay may be so small that only a general knowledge of reserves is necessary. Technical personnel are rarely employed by pegmatite mine operators to make such estimates. In the future, however, as capital outlay becomes larger, estimates of grade and reserves will have to be more accurate. Geologic Aspects of Determining Grade and Reserves Estimating grade and reserves requires that the type of pegmatite, the size and shape, and the internal structure be determined by detailed geologic mapping and careful mineralogic study. The wide variations in the texture and distribution of minerals within many pegmatite deposits make a thorough geologic study of this kind necessary before it is possible to decide what sampling methods should be used to determine mineral content or grade. Types of Pegmatites: The first step in economic appraisal of a pegmatite is to determine the min-eralogical and structural type. In general, pegmatites may be classified into two groups: 1) those in which component minerals are more or less evenly distributed throughout the entire body and show relatively minor variations in texture, and 2) those in which component minerals have been segregated into units with recognizable differences in texture, mineralogy. or both. Johnston" has classified these types of pegmatites as homogeneous and heterogeneous, respectively. Cameron et al.10 have used the terms ~inzoned and zoned for similar types. The difference between the homogeneous and heterogeneous types is of great commercial importance. Homogeneous pegmatites can seldom be mined where the products are concentrated by the hand methods now commonly used, but they have been mined in a few places where a milling process has

Jan 1, 1957

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By J. C. Febles

HISTORY. THE use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and .that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. bad been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore' had been uncovered and developed that copper sulphate began to appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 7, 1913

By P. H. Griffin

WHEN a subject, such as the manufacture and service of chilled car wheels, as has been fruitlessly discussed for ten or fifteen years, it is difficult to revive interest and action by the mere repetition of statements and arguments that have been made before. And when a situation involves serious responsibilities for conditions that have grown up under circumstances beyond the control of any particular individuals or authority, it is even more difficult to deal with. But there is one phase of every subject that need not involve these particular points if presented in a, proper manner; and that is, " the future state." I will try to present the subject of this communication from the latter standpoint and with the hope that all of those interested will feel disposed to give the matter attention from the basis that it is a, vitally important one to all that travel on railroads, whether as employees or officials, or as dependent on those in charge of the operation, or in the matter of materials and equipment used. The conditions of chilled wheel service have been changed so radically in the past ten or fifteen years by the use of freight cars of 40 and 50 tons capacity, that it is fair to say in the interest of all concerned in the use and in the manufacture of such wheels, that the increased strains and loads have been quite sufficient to account for much of the service results that have transpired. That proper provision was not made for increased possibilities of strength and wear, in fact that previous factors of the kind were allowed to deteriorate, is no proof that such wheels cannot be made equal to heavy service conditions as shown in the data given herein.

Jan 10, 1913

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By E. O. Jones

DURING the heating of cold-worked nickel silver, the tendency of the material to crack is well known. The present research deals with this question, and may conveniently be divided into the following sections: Changes in these alloys during heating and cooling, determination of the temperature at which cracking occurs, effect of grain size, quenching cracks, methods of overcoming annealing cracking. The work is far from complete, in particular the influence of impurities on this tendency has not been investigated, but the results so far obtained lead to certain definite conclusions, which are of theoretical and practical importance. CHANGES IN ALLOYS DURING HEATING AND COOLING During the annealing of many metals at a temperature just below that at which recrystallization sets in, there is evidence of some change, the effect of which is to harden and embrittle the material. This effect has been most clearly demonstrated in the cases of aluminum, copper, brass, and nickel silver, and appears to be a common property of cold-worked metals and alloys, or, at any rate, the non-ferrous ones. The effect would obviously offer an explanation for certain types of annealing cracking, but the trouble is so much more common in the nickel silvers than in the other alloys that some special cause should be looked for. There is, however, fairly good reason for believing that similar cracking may occur in some of the brasses; D. Bunting suggests that the a brasses toward the saturation limit are subject to a transformation closely allied in nature to that known to occur in the nickel silvers at around 320° C. Although the existence of this critical temperature range was known, it did not necessarily follow that this transformation was responsible for the trouble under investigation, so the first portion of this paper deals with the attempts made to determine whether other critical changes might not occur in these alloys. There were already reasons for the belief that such would prove to be the case, as the mechanical properties of the nickel

Jan 7, 1925

By E. A. Smith, E. R. Parker

METALLURGISTS and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applications and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. Single-crystal copper specimens were broken in tension at impact velocities up to 100 ft. per sec. The distribution of slip bands in the fractured crystals was found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. EXPERIMENTAL PROCEDURE Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were made into test bars by sliding threaded steel bushings over each end of a crystal and then flowing silver solder between the crystal and the bushing. The inside diameter of the bushings was slightly greater than the diameter of the crystals, to allow space for the silver solder. The bushings were placed so that the gauge length of the crystals was one inch. The assembly is shown in Fig. I, with two views of a fractured crystal. Annealed polycrystalline copper bars of similar shape were machined from solid stock. X-ray measurements were made on all single crystals to determine their orienta¬tions. The results are shown in Fig. 2, where the location of the axis of each specimen is indicated on a standard projection. The bars were broken in a commercial variable-velocity tension im¬pact machine, which has been described in detail elsewhere.7,8 The stress and strain were recorded by means of wire strain gauges and a special commercial oscillo-raph, also described in detail elsewhere.9,10 The equipment and method can be briefly described as follows. The impact machine consists of a motor-driven flywheel containing a two-pronged hammer. This hammer is held retracted in the flywheel

Jan 1, 1944

By G. R. Speich, Morris Cohen

The growth rate of bainite has been determined by hot-stage metallography in five hypereutectoid high-purity iron-carbon, iron-carbon-chromium, and iron-carbon-nickel alloys. The studies have been confined essentially to lower bainite. The growth rate is independent of time at constant temperature, but both the edgewise and sidewise growth rates increase with increasing temperature. Increasing the carbon content, or adding chromium or nickel, decreases the growth rate without greatly affecting the temperature dependence. The results lead to separate diffusion-controlled models for the edgewise and sidewise growth rates. ALTHOUGH bainite has been subject of many detailed investigations,1,2 the growth mechanism of this intermediate transformation product of steel remains unclear. One difficulty has been that practically all the kinetic measurements have been restricted to studies of the overall reaction rate. Only a limited amount of information3, 4-6 is available on the growth process itself. The purpose of the present work was to investigate the effect of time, temperature and composition on the growth rate of bainite using hot-stage metallography. This method makes it possible to observe continuously the isothermal growth of individual bainitic units because of the surface upheavals accompanying their formation.3 This information is needed to test the existing growth models and to obtain a better understanding of the factors controlling the bainitic transformation. EXPERIMENTAL PROCEDURE Alloys—The compositions of the alloys used in the present work are shown in Table I. The five alloys were vacuum-melted and cast, and were prepared from high-purity materials. The three iron-carbon alloys were available from the work of Roberts et al.7 in the form of 3/8-in. diam rods.* To facilitate machining, the rods were ing. The rods were then tempered for 3 hr at 650°C to allow machining. The iron-carbon alloys in Table I were selected for investigating the effect of carbon on the bainitic growth rate. Due to the rapidity of the transformations involved, it was not feasible to measure the growth rates in iron-carbon alloys having carbon contents much less than 0.9 pct C. The iron-carbon-chromium and iron-carbon-nickel alloys were selected to study the influence of chromium and nickel on the growth rate at a carbon level of about 1.1 pct C, since this carbon content was intermediate among the iron-carbon alloys. The concentrations of chromium and nickel were chosen to match isothermal trans formation diagrams in the literature.8'9 Hot-Stage—Since the iron-carbon alloys had such low hardenabilities, it was necessary to quench the hot-stage specimens drastically from the austentiz-ing temperature to the isothermal transformation temperature to prevent the formation of pearlite or proeutectoid constituents. A rapid-quenching metal-lographic hot-stage was built for this purpose. A maximum temperature of about 1100°C and quenching rates up to 500°C per sec could be attained with this equipment. The details of the apparatus are described in a recent publication. After being polished and mounted on the hot-stage, the specimen (0.020 in. thick) was protected from oxidation and decarburization during austenitizing by a vacuum of 10-4 to 10-5 mm. The quench to the reaction temperature was accomplished with a helium blast, and the isothermal run at this temperature was conducted in a helium atmosphere. A fine-wire thermocouple spot-welded to the sample and a high-speed

Jan 1, 1961

By C. W. Beattie, R. L. Solter

ALUMINUM-KILLED, low carbon steel sheets are used extensively for severe deep drawing and other difficult forming operations. They usually, but not always, have a characteristic grain structure in which the grains are elongated both in the lengthwise and in the transverse direction. As described by Burns and McCabe,&apos; a typical grain in the plane of the sheet has its two axes in that plane from 1 Y2 to 4 times as long as the axis normal to the plane of the sheet. Rickett, Kalin, and MacKenzieZ have also reported on the recrystallization behavior of such steel. The contrast in grain structures of fully processed sheets of aluminum-killed and rimmed steel is illustrated by Figs. 1 and 2. The elongated grain structure of the aluminum-killed sheet is not developed on all heats or lots of this metal, and studies of the factors controlling and influencing its formation are reported in this paper. Jeffries and Archerb tate that unstrained grains are normally equiaxed, but exceptions are common. For example, if a metal containing a material mechanically obstructing grain growth is subjected to considerable working followed by thorough annealing, it may exhibit grains consistently elongated in the direction of working. Our experiments demonstrate that aluminum-killed, low carbon steel is such a metal, and that the substance mechanically obstructing grain growth is aluminum nitride. The effectiveness of aluminum nitride in inhibiting grain growth has been found to be influenced by the degree of cold reduction, the rate of heating in annealing, the thermal history of the sample before cold reduction, and the residual aluminum content. A correlation between grain shape and austenitic grain coarsening temperature also was indicated and additional experiments demonstrated that aluminum nitride is also the principal cause for the fine grain characteristic of aluminum-killed steels. Manufacture In conventional practice, aluminum-killed sheet steel is manufactured from a low carbon steel containing approximately 0.02 to 0.07 pct residual (HC1 soluble) Al. With the exception of certain samples containing greater or lesser amounts of aluminum, the steels used in these investigations were within the following composition range: C, 0.03 to 0.06 pct; Mn, 0.28 to 0.38; S, 0.017 to 0.032; Al, 0.03 to 0.06; P, <0.01; and Si, <0.01. Properly heated ingots are rolled to slabs about 4 in. thick. After surface conditioning, the slabs are reheated to about 2300°F and hot rolled continuouslv to strip about 1/10 in. thick. The strip rolling is completed at a temperature of 1550°F or higher, and the strip is coiled, usually at a temperature near the lower critical transformation. After cooling, the strip is pickled to remove oxide, cold reduced 40 to 70 pet to final thickness, then annealed to 1250° to 1350°F in 20 to 80 ton charges, the size of which results in slow heating and cooling rates. Effect of Cold Reduction According to Sachs and Van Horn,&apos; the deformations of the individual grains in rolling are similar to those of the total volume. Thus individual grains would elongate in rolling according to the amount of cold reduction imposed. This is true theoretically, but as cold reduction increases the individual grains tend to fragment, and measured grain elongations become less than theoretical. The amount of grain elongation may be described by a numerical rating based on grain counts made by the intercept method. Specimens are polished normal to the plane of the sheet, with the polished surface extending parallel to the rolling direction. After etching, grain intercepts are counted along a 50 mm line on a micrograph of suitable magnification. In random locations parallel to the plane of the sample 20 counts are made and 20 are made in the thickness direction of the sample the average count in the thickness direction divided by the average count parallel to the plane of the sample gives a numerical rating of the grain shape called grain elongation. For example, a grain elongation of 2.00 means that the average grain is twice as long as it is thick. The average of both counts may be converted to grains per sq mm by a nomograph relating intercept counts and grain count. By the same procedure the grain elongation in the plane of the sheet but transverse to the rolling direction may be determined, using transverse metallographic samples. A comparison of theoretical and measured grain elongation was obtained on an aluminum-killed

Jan 1, 1952

By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By MARIUS R. CIMPBELL, Edward W. Parker

DESCRIPTION. ACCORDING to the estimates prepared by the U. S. Geological Survey, the area underlain by workable coal-beds in the United States is 496,776 sq. miles. Of this total area, 480 sq. miles contain the entire anthracite coal-fields of Pennsylvania. The bituminous coal-fields are estimated to be contained in areas aggregating 250,051 sq. miles. The grade of coal between bituminous and lignite, and which is designated by the Geological Survey as " sub-bituminous," is estimated to be contained within areas aggregating 97,636 sq. miles, while the areas containing lignite aggregate 148,609 sq. miles. The coal-fields are divided, for the sake of convenience in classification, into six main provinces, as follows: 1. The Eastern. Province, containing the anthracite coal-fields of Pennsylvania and the bituminous coal-fields of the Appalachian region-namely, those of western Pennsylvania, Ohio, Virginia, West Virginia, Kentucky, Tennessee, Georgia, Alabama, and small outlying areas in North Carolina. 2. The Interior .Province, containing the bituminous coal-producing regions of Michigan, Illinois, Indiana, western Kentucky, Iowa, Kansas, Missouri, Oklahoma, Arkansas, and Texas. 3. The Gulf Province, containing the lignite-areas of Alabama, Mississippi, Louisiana, Arkansas, and Texas. 4. The Northern or Great Plains Province, containing the lignite and sub-bituminous areas of North and South Dakota, eastern Montana, and northeastern Wyoming. 5. The Rocky Mountain Province, containing the bituminous and sub-bituminous areas of western Montana and western Wyoming, Colorado, Utah, and New Mexico. 6. The Pacific Coast Province, containing-the areas of Washington, Oregon, and California.

Apr 1, 1909

By A. M. Kivari

OPERATIONS at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hydroseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the manufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. [t] About 3130 tons of limestone, 620 tons of clay and 100 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. Up to the present time, the corporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modified-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Redding, Calif., the total demand being 5.800,000 bbl. of cement. Following are some of the cement require¬ments of the Shasta Dam specifications: [PER CEN&apos;I Chemical composition: Loss in ignition2.25 Insoluble residue0.75 S032.25 M905.00 Uncombined lime in clinker (CaO)T.25 Percentage of iron oxide to alumina ratio1.5 Compound composition: Tricalcium silicate (3CaO.Si02)Not more than 35 Dicalcium silicate (2CaO.Si02)Not less than 40 and not more than 6,5 Tricalcium aluminate (3CaO.Al203)Not more than 7 Tetracalcium aluminoferrite (4CaO.A1203.Fe203) Not more than 20 Fineness:] The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following: [ ]

Jan 1, 1941

By G. H. Clevenger

The reagents now used in flotation consist of various acids or salts, which may be either electrolytes or non-electrolytes, dissolved in water and some substance or combination of substances which function as collecting or frothing agents. At times the only dissolved salts present are those naturally occurring in the water used. The general effect of the electrolyte is to greatly sharpen the separation between the gangue and the concentrate. Examples of this are: The use of sulphuric acid with zinc ores; and of sodium carbonate or calcium oxide (lime) with silver-gold ores. Crude pyroligneous acid is also sometimes used when avail able. Various oxidizing agents, such as permanganates, bichromates, etc., are added in the selective flotation of lead-zinc ores. Many other reagents for performing certain specific functions, either real or imaginary, have been proposed, and a number of them have been tried upon a working scale. The wild orgy of experimentation which is now going on in flotation exceeds even that which followed the introduction of the Washoe process for the treatment of Comstock ores, when, among other things, sage-brush tea and tobacco juice were reagents added to the pans. Out of all this will, of course, eventually come a more or less standard practice for the treatment of each class of ore. Omitting a discussion of the functions of frothing and collecting agents, the reagents used in flotation for this purpose may be classified under five general heads: (1) Essential oils; (2) fixed or fatty oils; (3) alcohols and their combinations with organic acids; (4) coal tar and its refined products; (5) petroleum and its refined products. A flotative agent of some kind is required in flotation as now practiced. A single reagent, as, for example, certain of the essential oils, may perform the dual function of frothing and collecting agent, or a mixture of substances may be required. In this country, the essential oils used have been wood products, and have been almost exclusively confined to the steam-distilled pine oils. At the present time, the supply of these is limited, and the cost almost prohibitive, so that their use has been dispensed with as far as possible. The oils and tars resulting from the destructive distillation of

Jan 1, 1917

By Charles B. Forgan

THE Stan Trg ore body now being exploited by Trepca Mines, Ltd., originated by the metasomatic replacement of limestone and consists mainly of an intimate mixture of sulfides associated with little admixed gangue. The chief sulfides are galena, marmatite, pyrite, and pyrrhotite. Geological structure, embracing both igneous and sedimentary agencies, exerts important control on ore deposition and presents many features of great interest. Geological Formations and Intrusives Stag Trg Series-The dominant formation is the Stan Trg series, which

Jan 1, 1936

By J. A. Danko, C. D. Pears, L. D. Schmidt, J. P. McGee

This paper describes a pilot plant built on the campus of West Virginia University by the Federal Bureau of Mines station at Morgantown, West Virginia, for gasifying pulverized coal in a mixture of oxygen and steam at pressures in the gasifier up to 450 psig. The work upon which this report is based was done under a cooperative agreement between the Bureau of Mines and the West Virginia University. The goal of Bureau of Mines work at Morgantown is development of a low-cost process for producing mixtures of carbon monoxide and hydrogen for the modified Fischer-Tropsch synthetic-fuel plants, which may be shifted to produce hydrogen for coal-hydrogenation plants. Gasification with oxygen offers the inducement that the gas may be generated at the pressure at which the gas will be utilized in a gas-synthesis plant. Since the optimum pressure for the synthesis appears to be about 400 psig, the gas should be produced at approximately 450 psig to take care of pressure drops in the purification train and control valves. If the gas is generated at the pressure of utilization, only the oxygen need be compressed, not the raw synthesis gas. This means a saving in power of 5 hp per hour per 1000 cu ft (CO + H2), which is approximately a saving of 4 cents per gallon of gasoline. For example, consider a commercial plant generating 18,000,000 standard cubic feet per hour of raw gas that would produce approximately 10,000bbl of liquid product per stream-day. Assume that this gas would be 85 pd CO + H2 and that the oxygen required would be 320 cu ft per 1000 cu ft of CO + H2. The following estimate is based on a commercial centrifugal compressor. If the 18,000,000 std cu ft per hour of synthesis gas is compressed to 450 psig with 74 pd efficiency, 107,000 hp is required for compression. If the synthesis gas is generated at 450 psig pressure, only

Jan 1, 1953

By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.&apos; The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.&apos; In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."&apos; The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory&apos; shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.&apos; Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation&apos; in previous work with high purity aluminum.

Jan 1, 1957

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty &apos;metallic&apos; orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By Robert M. Jimeson

At the recent SME Fall Meeting in Salt Lake City, Robert M. Jimeson, Physical Science Administrator of the U.S. Bureau of Mines, cited the research programs underway in the Bureau&apos;s Division of Coal Research, and outlined their current status. These research programs have been selected by the Division because of their relative value and high probability of success in contributing to the conservation of the Nation&apos;s coal and to the expanded use of coal in current or new markets. Since about 50% of coal consumption in the United States is in the production of electric power, 20% in production of metallurgical coke, and over 20 % by industry in producing process steam and power, the Bureau has placed much emphasis on research that will maintain coal&apos;s leadership in these established areas. This emphasis is reflected in the projects discussed on these pages. Bear in mind that this survey is not all-inclusive. Other projects underway include studies on furnace performance factors, improved burner design, and other critical boiler work which can be used immediately by industry to improve efficiency of current practices in power generation; other investigations are aimed at reducing fireside deposits and corrosion of boiler and super- heater tubes, fly ash utilization, and control of SO, from flue gases (a major step in preventing air pollution). These plus many other projects during the past years have served to focus attention on the fact that the U. S. Bureau of Mines is presently making the largest single contribution to this Nation&apos;s coal research effort.

Jan 11, 1963

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