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By G. C. Gambs

The electric utility industry is the largest customer of the coal industry and consumes nearly 50% of the present coal production in the United States. The byproduct of the burning of coal in utilities is ash in several forms including fly ash, bottom ash and bottom slag. At present, very little of the coal ash produced is being used and must be disposed of as waste. The coal industry should look upon this waste material as a valuable by-product which, if it can be sold for $2 to $4 per ton, will have the net effect of reducing the cost of coal to the utility by 1¢ to 2¢ per million Btu. There are many ways to use coal ash and thus benefit both the coal industry and the electric utility industry by reducing the cost of coal as burned. The solutions to the problems are obvious and all we have to do is apply them. The electric utility industry is the largest customer of the United States coal industry, consuming nearly 50% of present coal production. By 1980, the electric utilities are expected to burn over 500 million tpy of coal or 75% of total coal production. When coal is burned in electric utility plants, ash is produced in one of several forms. These include fly ash, bottom ash and bottom slag. At the present time, approximately 20 million tons of these ashes are produced and must be disposed of by the utilities at a cost of 50¢ to $2 per ton. In 15 years, more than double this quantity will be produced. Only a small quantity of this ash is put to any practical use. Much remains to be done about expanding uses for fly ash and bottom slag. It is well known that fly ash, when used to replace a portion of the cement in a concrete mix, will produce highest quality concrete. The Corps of Engineers and the Bureau of Reclamation have constructed dams and other concrete structures for years with fly ash as a partial replacement for cement. However, many construction firms do not use it. This can become an opportunity for the coal industry to reduce the cost of coal delivered to utilities. Any fly ash, or other ash or slag, which is sold by the utilities, reduces the cost of coal burned by the utility. As much as 1¢ to 2¢ per million Btu could be taken from the fuel cost for each ton of ash sold which otherwise must be disposed of at a cost.

Jan 1, 1967

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By L. F. Terry, H. K. Ihrig, D. J. Sabin, Ralph E. Davis

This paper presents the results of a study of the comparative values of the several fuels commonly used by industrial plants. It shows that the energy actually recovered from any fuel and turned into useful work is dependent upon several factors: (1) the total energy available in the fuel, (2) energy losses resulting from combustion reactions and (3) energy losses dependent upon the mechanics of the firing operation. The chemistry of combustion and the losses resulting therefrom are discussed. The Advantages and disadvantages of the several mechanical methods of firing and the resulting heat losses in each are developed. Data obtained from several typical fuel operations, where careful records have been maintained, are presented to show that the practical results in the actual operation are in harmony with the theoretical results developed in the earlier part of this paper. Water power and solid, liquid or gaseous fuels are at present the only commercial sources of energy. The economic utilization of any one of them depends, in the final analysis, on the cost of energy per unit of finished product to which the energy is applied. The location of the plant utilizing the particular fuel chosen is a large factor in the original choice. The cost per unit at its original natural source, or even in its delivered form, is not always the final measure of its worth. The use of electricity as a source of energy illustrates this to the extreme. Electric current produced from water power is very cheap in certain localities. In Norway, current is sold as low as ½0# per kw-hr., while in dry cells it costs as much as $10 per kw-hr. Yet the sale of dry cells is a large business. The selling price of gas also varies widely. In some localities natural gas for the manufacture of carbon black sells for as low as $0.02 per million British thermal units, while artificial gas for domestic purposes sells for as high as $6 per million B.t.u. Obviously the cost per unit of energy is not the final determining factor in its purchase. Any discussion of the economic utilization of fuels must include costs in relation to the units of finished material manufactured. In large central power generating stations, this is the over-all cost per kilowatt-hour, and in ceramic firing the cost per unit of finished product of a certain quality is the criterion of economic utilization.

Jan 1, 1931

By M. Gensamer

ONLY recently has it been realized that preferred orientations are common in hot-rolled steels. In a recent paper, N. P. Goss1 stated that hot-rolled mild steel exhibits a texture different from that charac-teristic of cold-rolled steel. No complete study of these hot-rolling textures has been reported using the pole-figure method of Wever. The material used in the work reported in this paper was the same material used by Gensamer and Mehl2 in a recent study of preferred orientations in cold-rolled steel, to which reference may be made for the composition and thermal history of the steel. Automobile-body sheet bar, 4 in. thick was hot-rolled at two temperatures, 780° and 910° C. (1436° and 1669° F.). (These temperatures refer to the tempera-ture of the furnace in which the steel was heated.) After each pass the steel was returned to the furnace and held there long enough to return to temperature. Although no accurate method was used to measure the temperature after each pass, it was estimated by color that only a slight drop in temperature occurred. In order to determine the effect of any preferred orientation that might have persisted through the normalizing treatment, one specimen at each temperature was rolled in the same direction as the original working direction and the other at right angles to it. The total reduction in each case was 85 per cent, the specimens having been reduced from 0.250 to 0.0375 in. in five passes. Final cooling was in air. Pinhole reflection photograms were taken of all four specimens, with the rolling direction vertical and the X-ray beam at an angle of 7° with the transverse direction (the transverse direction is defined as that direction in the rolling plane perpendicular to the rolling direction). These photograms, taken with a Me target at 35 kv., are reproduced in Figs. 1, 2, 3 and 4. They show that a more pronounced texture was developed by the low-temperature rolling (780° C.), and that of the two

Jan 1, 1936

By R. L. Stegman, M. R. Achter

Nickel, fatigued in vacuum, shows intragranular crack initiation and growth at low temperatures. An increase in temperature initially prolongs fatigue life due to a more homogeneous distribution of slip. With a further temperature increase, the mode of failure undergoes a transitiotz to intergranular crack initiation with concurrent recrystallization which results in a shorter life. The transition temperature varies with bending strain and specimen purity. UNTIL recently, very little work has been done on the effect of temperature on the mechanism of fatigue and the resultant variation in fatigue life. Except for mild steel, where strain aging raises the strength at moderate temperature, fatigue lives had been shown to decrease with an increase in temperature. In their review article, Allen and Forrest' summarized the work of McCammon and Rosenberg and of Forrest and Mann on the fatigue of copper from -269" to 325°C. The fatigue life vs stress curves remained roughly parallel over this temperature range, the fatigue strength decreasing progressively with increasing temperature. When testing was done in vacuum, the present authors' found the results for nickel were different from those quoted above. Initially, the fatigue lives increased with temperature and then decreased as a grain boundary mode of failure was observed. The initial increase was attributed to a more homogeneous distribution of slip, a condition which was not as conducive to crack initiation as the bunching of slip lines observed at 20°C. Ronay, Reimann, and wood3 observed a similar change of slip line distribution in brass, tested in air, with rising temperature. Our previous observations were based on preliminary work with relatively few specimens, fatigued at comparatively low strains. To learn more about the mechanisms, the present investigation was undertaken for the purpose of studying systematically this effect over a wider range of strains and as a function of purity of the nickel. EXPERIMENTAL PROCEDURES The testing equipment, procedures, and specimen geometry have been described elsewhere.' An optical technique to measure bending strains was used as de-

Jan 1, 1968

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By George Mieyr, H. M. Ziesemer

Prior to 1909 that mountain of porphyry known as Sacramento Hill had hardly been touched though it had always been thought to contain ore. During that year, exploratory work was started by underground methods; drifting and raising continued until 1913. It was proved that a mineralized zone existed, the limits of which had not been determined ; so, because of the lower costs of exploratory work and the greater desirability of vertical sections, it was decided to prove the extent of the ore zone by churn drills. Drilling continued until 1917, when it seemed almost certain that the horizontal limits of the orebodies had been determined. Ore continued in depth in one direction beyond a point where it was economical to explore by churn drilling; this extension is still being developed by underground methods. The irregularities of the boundaries of the ore zones, together with the variable grades of ore encountered, made it necessary to drill on the corners of 100-ft. squares. Two ore zones were proved, known as the East and West Orebodies. The Sacramento Hill porphyry stock intruded into the Dividend fault. The fault ran roughly east and west with a dip to the south, having pre-Cambrian schists on the north against Paleozoic limestone on the south. This intrusion was accompanied by a silica breccia on the south periphery, along the limestone contact side. The ore lay in the silica breccia and in the porphyry, some distance from the breccia. NO ore was found in the heart of the porphyry mass on the north side, along the schist contact. The West Orebody is elliptic in shape, having a major axis of 1200 ft. (366 m.) and a minor axis of 800 ft. (244 m.); these diminish with depth until, at 300 ft., the axes are 500 ft. and 300 ft., respectively. The ore consists of chalcocite, some bornite, chalcopyrite, and considerable pyrite in a siliceous gangue. About 30 per cent. of the copper is caused by

Jan 1, 1923

By J. Ruzicka

In creep testing, material is subjected to a constant load, preferably at a constant temperature, and its rate of deformation is measured. The method of loading can be of various types but in this paper only creep testing under tensile load will be considered. The ordinary tensile test is essentially a comparison test in conditions that frequently hear little or no relation to those under which the test material is to be used in service. The purpose of creep tests is to measure the strength of the test material at slow rates of deformation that more nearly approach the rates realized in service. One purpose of this paper is to illustrate that the creep test, in addition to its value as a service test, is superior to the ordinary tensile test as a sensitive tool for the comparison of certain metals in investigative testing. The other purpose is to describe equipment having distinctive features of design that make it especially suitable for such tests. Representative data obtained with this equipment on a group of rolled zinc-base materials are given. These data are compared with those from practical comparison tests of the creep type on weatherstrip fabricated from the same group of materials. The comparison illustrates the value of the fast creep test and of the equipment. The Equipment The creep equipment consists essentially of a tank containing a constant-temperature oil bath in which the creep of 14 specimens, loaded by means of levers, is measured by means of one movable extensometer. Figs. 1, 2 and 3 illustrate its general construction and appearance. Constant-temperalure Oil Balh.—A common constant-temperature bath requiring only one temperature-controlling equipment for a number of specimens was chosen as the best means of fulfilling the requirements of low cost and compactness. In addition, this allows the testing of a group of specimens under identical temperature conditions.

Jan 1, 1937

By R. I. Jaffee, F. C. Holden, H. R. Ogden, A. G. Imgram

The tensile and notch tensile properties of four refractory metals (molybdenum, tungsten, niobium (columbium), and tantalum) and one alloy (Mo-0.5Ti) were investigated. All the materials were evaluated in bar form, and the molybdenum and Mo-0.5Ti also were studied in sheet form. The notch sensitivity of each material was evaluated on the basis of several criteria, including the notch-unnotch strength ratio, the ductility transition, and the fracture transitions. USE of refractory metals as structural materials in aircraft and space vehicles may subject them to low-as well as high-temperature environments. At elevated temperatures, the usefulness of a material usually is limited either by strength considerations

Jan 1, 1962

IN A broad sense, the subject of slag control includes not only the adjustment of the composition of the slag but also of its relative weight in terms of percentage of the metal-bath weight. The slag is made up essentially of (1) oxides formed by oxidation of silicon, manganese, phosphorus, and iron in the charge, (2) SiO2, MnO, and other oxides charged as such, and (3) lime charged or fed to the heat to neutralize the “acidic”: oxides present (Si02 and P2O5). Obviously, if practically perfect control were possible over the composition of the charge as well as over the oxidation process during the melting period, both slag weight and composition would be very nearly predetermined, and the control problem would be solved. Unfortunately, we have only a somewhat. imperfect control over these factors, so that beginning at about the lime-boil period in the heat, and later in the early refining period, it becomes necessary for the first helper, as the heat progresses, to make quick estimates of the composition and physical state of development of the slag (as well as of the amounts of phosphorus, sulphur, and carbon in the metal) from which he can judge how much extra lime, roll scale, fluorspar, and other additions will be needed not only to give the desired final slag composition, but also to hasten the complete fusion or shaping to a desired viscosity in the liquid state. The discussion in this chapter is limited essentially to those more or less practical rapid methods of slag estimation that have been used, or at least tried, for these purposes under actual open-hearth shop conditions. Another aspect of importance here is the extent to which the freedom of choice to the operator is limited by available charge materials, product specifications, and the oxidation and other chemical- reaction effects which inevitably occur under the conditions of this furnace process. For a better understanding of these control limitations and of the chemical and physical background of the subject, the reader is urged to read at least part of the discussion in Chapters XVII and XIX. Charge materials are discussed in Chapter IV, and many of the details of charging, melting, and refining practice closely related to slag control are given in Chapters VI and VII.

Jan 1, 1944

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By Robert Mehl

PART I. ORIENTATION RELATIONSHIPS IN OXIDE LAYERS Oriented overgrowths and intergrowths among both metallic and nonmetallic substances have been recognized and studied for well over a century. The work of Widmanstätten in 1808 on the geometrical struc-ture in meteorites, a structure known by his name, demonstrated that oriented intergrowths can occur in purely metallic systems. This fact led to much of the early microscopic study of alloys, contributing greatly to the advance of physical metallurgy. The problem has been attacked again in recent years in a comprehensive fashion, with the object of dis-covering what atomic movements may occur during phase changes in alloy systems. Much of this work has appeared in the A.I.M.E. TRANS-ACTIONS in a series of papers published by Mehl and coworkers beginning in 19311. Although many aspects of this general problem remain unsolved, it may be said that the orientation of a new phase forming by precipitation from solid solution or by transformation invariably bears, a unique relationship to the orientation of the phase from which it formed, and that similarity in atomic patterns on atomic planes in the two phases play an important part in determining the orientation relationship. Analogous orientation relationships exist in oriented intergrowths in nonmetallic systems-mineral or inorganic. In 1827 Haidinger2 dis-covered natural intergrowths of hematite and magnetite, and demon-strated that the rough form of the magnetite octahedrons was delineated by small crystals of hematite, of which the basal (00.1) planes lay parallel to the octahedral cleavage planes of the magnetite. The description of this orientation relationship was later completed by von Rath3, who showed that the edge (00-1):(10-1) in hematite lies normal to the [111]

Jan 1, 1937

By R. L. Klueh, W. W. Mullins

During the course of a study on the periodic precipitation (Liesegang phenomenon) of water vapor bubbles in solid silver, some interesting observations were made concerning the formation and growth of these bubbles. Under certain conditions it was found that the bubbles which formed in the single crystals led to the formation of large blisters ad cracks, and when poly crystalline specimens were used grain boundary cracking was observed. These two phenomena were examined in some detail, and it was found that an important step in the formation of the blisters and grain boundary cracks was the impingement of neighboring bubbles. DURING the study of Liesegang precipitation in solid silver,' some interesting observations were made concerning the formation and growth of water vapor bubbles. The bubbles were formed by annealing oxygen-saturated silver in hydrogen. Because of the similarity of this phenomenon to the hydrogen embrittlement of tough pitch copper,' it is known in the literature" as the hydrogen embrittlement of silver. In some respects it appears that the hydrogen embrittlement of silver is similar to the processes of hydrogen attack of steel5 and blister formation.' Hydrogen attack results from the high-temperature reaction of hydrogen with dissolved carbon or carbides in the steel to form methane (usually at grain boundaries). Blister formation occurs in steel and other materials as a result of hydrogen produced by corrosion, pickling, and so forth. Because of these similarities, some speculations were made concerning these other processes. EXPERIMENTAL PROCEDURE Water vapor bubbles were formed in 99.999+, 99.99+, and 99.9 pct Ag by annealing in a partial pressure of oxygen (pq) until saturated and then in a partial pressure of hydrogen (pH,). The hydrogen diffuses into the silver and reacts with the dissolved oxygen to form water vapor which precipitates in the form of bubbles. The specimens were then sectioned, silver-plated, mounted in cold-setting plastic, ground and polished through a preliminary polishing, and finally chemically polished.' The bubbles were visible without etching.

Jan 1, 1969

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.' It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By S. F. Emmons

The first paper which appears in the published Transactions of our Institute is that read by our respected Secretary at its first meeting in Wilkes-Barre in May, 1871. It is entitled " The Geographical Distribution of Mining Districts in the United States," and presents a brief but masterly review of what was known of the distribution of our deposits of useful minerals, particularly the metals, not only from a geographical but from a geological stand-point. At the request of Dr. Raymond I agreed, somewhat hastily, perhaps, to write for this occasion a brief sketch of the geological distribution of the deposits of the useful metals in this country, in the light of the increased knowledge of the present day. In the time given no personal investigation was possible, and as it was therefore out of the question to attempt to make anything that could be considered an original contribution to the history of our ore-deposits, I have been obliged to limit myself to an examination of such pub-

Jan 1, 1894

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic 'quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen' is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,' and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,')' silicon nitride,8 and vanadium nitride,' titanium carbide,'' and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.' This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By E. S. Grumell

The correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbreviations will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution. Section 1.—Cost It has often been stated that the cost of sampling should bear some relationship to the value of the product, and since coal is a relatively cheap raw material it would be a major error to specify, for ordinary commercial purposes, elaborate and costly methods of sampling which nobody would adopt. Specifications must be of such a nature that they will be used. We believe that one of the achievements of the last 10 years has been to reduce the cost of sampling. There is, however, another point to be considered; via., that the cost of sampling should bear some relationship to the value of the investigation. Correct sampling is a cog (possibly a small one) in the wheel

Jan 1, 1940

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By L. L. Handy

Two equations are compared for calculating imbibi-tion rates of water into porous media. A linear relation was found to apply when the square of the volume of water imbibed was plotted against time for water imbibing in natural rock materials. The effect of adsorbed organic materials on surface wettability was determined from measurements of rate of imbibition, water saturation and water permeability. INTRODUCTION An understanding of the mechanisms by which water displaces oil from porous media requires an understanding of the role of capillary forces in the displacement process. The capillary forces are determined by properties of the water-oil-solid surfaces. Consequently, some measure of the surface properties of reservoir rocks is necessary if displacement behavior in oil reservoirs is to be predicted from laboratory measurements. Several experimental procedures have been proposed to assign quantitative wettability indexes to reservoir rock surfaces. The most recent of these proposals are those of Bobek, Mattox and Denekas' and Amott.' These indexes are designed to show a continuous variation from the preferential oil-wet to the preferential water-wet systems. They require measuring some property of the rock which is a function of surface wettability. The quantities are measured on unaltered core material and compared with values obtained for known oil-wet and water-wet extremes on the same material. These methods are useful but are semi-empirical in nature. They have the disadvantage that the measured quantities may be functions of other variables in addition to surface wettability. Some understanding of the behavior of water-oil-rock systems may be obtained from studies of the simpler water-air-rock systems. Surfaces of a given wettability are more easily maintained for the latter. Also, certain approximations can be made for the flow of water and air which are not justified for water-oil flow. The theoretical and experimental work discussed in this paper is part of a study of the role of capillarity in the dynamic displacement of air by water. The expec- tation is that observations for the water-air system will lead to generalizations which are applicable to water-oil systems. THEORY Imbibition is defined as that process by which one fluid displaces another from a porous medium as a result of capillary forces only. Differential equations have been derived to describe the displacement of oil by water during imbibition, but these equations have not been solved.".' With certain assumptions, however, solutions are possible for water-air imbibition.

By C. M. Loeb, T. E. Norman

THE use of ball, rod and tube mills for grinding ore, cement and other materials has grown so rapidly during the past forty years that the world's annual consumption of ferrous grinding media for these mills is now estimated to be between one half million and one million tons per year. Ferrous grinding balls constitute the major portion of this tonnage. Obviously they represent sufficient value to justify thorough studies' of the factor sgoverning their performance. The selection of grinding balls is governed principally by: I. Quality (wear resistance, impact resistance, soundness, and the like). 2. Sources of supply and delivered cost. 3. Grinding characteristics or efficiency in the ball mill. This paper deals principally with the quality of ferrous grinding balls. In the study of these factors certain data relative to the fundamental nature of ball wear in ball mills have been obtained. These data are also presented and discussed briefly. THE DEVELOPMENT OF A SUITABLE WEAR TEST A study of the fundamental factors governing the quality of grinding balls has been hampered seriously by the fact that a competent test has, in the past, involved the purchase of several hundred tons of balls of a specific type which were then run in one or more ball mills for a period ranging from several months to several years' duration. Often, during the period of test, it became necessary to change operating conditions or the character of the ore fed, to the test mill with the result that the rate of ball consumption changed and the test figures became of little value. Under such circumstances, progress in the development of better grinding balls, has been necessarily slow. Economic factors and variations in the quality of balls produced by different sources of supply generally make it necessary for each mill operator to determine for himself the most suitable type of balls for his mills. In our own ball mill grinding operations at Climax, Colo., we were faced with this problem. After we had run a few large scale wear tests at considerable expense we decided to investigate the possibilities of a small scale wear test which would be capable of testing numerous types of balls within a relatively short time. The most important requirement of any test is, of course, that it give results which can be used to predict accurately the wear in full scale operations. It was known that Ellis and his associates1,2 had developed a method of testing grinding balls by small scale tests run at the Ontario Research Foundation. Ellis' method of testing was used as a starting point in our investigations. In the course of our tests a number of modifications of the original method were found to be desirable so that, by an evolutionary procedure, a method of small scale

Jan 1, 1947