Search Documents

By ARTHUR S. DWIGH

Discussion of the paper of W. W. NORTON, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 92, August., 1914, pp. 1993 to 1999. ARTHUR S. DWIGHT, New York, N. Y.-Mr. Norton's chief argument is directed against the idea that the D. & L. sinter is any better material for the blast furnace than the H. & H. product. He supports this by citing two experimental furnace runs. Reducibility.-To discuss a furnace record like that quoted by Mr. Norton for the five days' run in August, 1912, is manifestly difficult for an outsider, but a possible explanation for the poor reduction on Furnace No. 5, smelting D. & L. sinter, may lie in the fact that both sets of furnaces carried the same fuel charges. Other things being equal, if 11 ½ per cent. coke was right for the furnaces smelting H. & H. product, it Was too much for the furnace smelting D. & L. product, as I shall endeavor to show later, and incipient overfire, accompanied by higher leads in slag and matte, was induced. It may sound like a paradox to say that excessive fuel sometimes produces poor reduction, but it is a sad fact. In certain plants where practically the entire charge to the blast furnaces receives a preliminary treatment by being sintered on the D. & L. machines the peculiarities of this problem have had to be very carefully studied, for serious metallurgical difficulties presented themselves when the change was first made to D. & L. sinter in large quantities. Some of these plants had blast pots before they had D. & L. machines, and many opportunities were afforded for comparative study of this very point. There is reason to believe that, clue to the long period of blowing and the higher temperatures developed in the pots from greater mass action, the iron in the H. & H. product is present chiefly as Fe203, perhaps in the form of ferrites, while in the D. & L. product the iron is present as FeO. The fuel charge in the blast furnace must be so proportioned as to exactly meet the chemical and thermic requirements of reduction and melting. If ally of these functions have been performed before the material enters the furnace, a corresponding allowance should be made or the fuel balance will be disturbed and bad work will result. One of the functions of the coke is to reduce enough metallic Fe for the matte requirements, leaving the remainder of the iron as FeO to go into the slag. In smelting almost any other material than D. & L. sinter the iron must-be reduced from the higher oxides, Fe203 or Fe304, to the protoxide, FeO, before a true comparative basis is reached. Experience has shown that with about one-half D. & L. sinter on the charge the coke should-be cut about 10 per cent. This theoretical benefit is borne out by the practical blast-furnace results on a large scale in numerous plants. In fact, wherever this very important factor is ignored the evil symptoms of excessive fuel will be indicated,

Jan 11, 1914

By Franz Fohr

On July 27, 1919, there passed away a simple, unassuming gentle-man, who, throughout his life, allowed his intense modesty to keep him-self in the background and during his later years effaced himself so thoroughly that but few of his acquaintances knew aught of him. Yet he was one of our accomplished metallurgists, who did good work in the practice of his profession and lived an upright life. Now that he is no longer with us Franz Fohr cannot plead to be overlooked, and those who fondly remember him will be gratified by his receiving his due. Franz Fohr was born, Sept. 7, 1838, in Mannheim, Germany. Of his ancestry, education, and early career we know scarcely anything. We do not even know just when he came to America, or. what led him hither. The first record of his professional work in this country, found among his papers, shows that from July, 1870, to Jan. 1, 1872, he was superin-tendent of the Newark Smelting & Refining Works, then owned by Ed-ward Balbach & Son. At that time the Balbach works at Newark, established in 1850, and the Selby works at San Francisco, established about 1866, were the only important silver-lead refineries in the United States. Mr. Fohr may have been associated with the Balbachs for some time before he became superintendent of their plant or he may have come from Germany but a short time previously. At all events, it is certain that he was at that time an experienced and accomplished metallurgist. After leaving Newark and going to San Francisco, he soon formed a connection with Thomas H. Selby & Co. Early in 1874-this firm sent him to New York to procure information respecting the manufacture of white lead. His engagement in New York terminated on-Jan. 31, 1875. During 1875, Mr Fohr spent some time at Silver Islet and in the Lake Superior copper region, but of his work there no record remains. In the latter part of 1875, or early in 1876, he associated himself as metallur-gist with the Boston Silver Co., operating at Saint John's, Summit County, in which William L. Candler, of Boston, was the moving spirit. That company was developing its mine in 1875. At the end of that year it "had about 800 tons of ore on hand, about three-fourths of which is dress-ing ore, to be concentrated in its very systematic establishment and to be smelted into pig lead." Evidently Mr. Fohr was engaged for the latter purpose. Henry A. Vezin, erudite and painstaking, was the mechanical engineer for the company. In the fall of 1876, Anton Eilers took his family for the first time so far West as Denver and Mr. Fohr went with them. I do not think that Mr. Eilers had any connection with the Boston Silver Co., save possibly in a consulting capacity, but he visited Saint John's and the enduring friendship among Eilers, Fohr, and Vezin, which terminated only with their deaths, dated from that time.

Jan 12, 1919

By John D. Sullivan, Chester R. Austin, Edwin J. Rogers

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By P. H. Delano, Will H. Coghill, G. D. Coe

Data concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as " grindability-index numbers," but grind-ability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pull'erized product by a method comparabLe with- commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulvcrizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation,it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-¾-inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horsepower-hours." The channel-roller pulverizer hereinafter described is believed to meet these requirements. History oF the Machine The, work started when Ralph W. smith, engineer, St. Genevieve Lime Co., St. Cenevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasive-ness of dentifrices,1 and it was thought the same principles might be applied to coal, Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By W. H. Hough, P. B. Leavenworth

Development during 1942 led to the discovery of 26 new fields in the Texas Gulf Coast, as compared with 27 during 1941. Of these, 19 are classed as oil fields, 4 distillate fields, and 3 gas fields. Production from the new fields amounted to 614,467 bbl. to October 1942. Producing Sections.—Discoveries in I942, compared with the previous two years, classified by producing formations, are shown in the following table: It is interesting to note the increase in Wilcox discoveries due to the extensive geophysical campaign that has been con. ducted since 1940. Drilling.—During the year 688 wells were drilled, of which 574 produced oil or gas and 114 were dry. This represents a considerable decline in activity over the previous year, when 1405 wells were drilled in the area, of which 1081 were producers and 324 failures. Jackson County continued to hold the lead, with 222 wells completed. Production.—-Despite curtailed drilling, production amounted to 118,009,451 bbl. for 1942, indicating a slight increase over the 113,726,893 bbl. produced during 1941. The statistics in Tables I and 2 include condensate and distillate as oil production, because many Gulf Coast fields produce oils with a wide variation of specific gravities, all of which are commingled in pipe lines. Table 3 shows by counties most of the activities referred to. The number of wells drilled includes only field wells; not wildcats. Outstanding Fields of 1942 The Texas Gulf Coast covered in this report has 270 more or less active oil and gas fields, including the new discoveries of 1942. Of these the most outstanding from the standpoint of production are listed in Table 4. Each of these fields produced one million barrels or more during 1942. Some of the fields where new extensions are occasionally referred to as separate fields, such as West Columbia and New West Columbia, or Thompson and South Thompson, are combined to give a more accurate outline. Two interesting facts may be noted from this list of some 26 oil fields: (I) that the Lolita field, Jackson County, is the only discovery since 1938 to produce more than one million barrels annually, although there have been 79 discoveries since Jan. I, 1940; (2) that 20 of these 26 fields produce from the Frio. New Fields ALief, Harris County.—Pure Oil Company's No. I Mike Albanese was drilled to 8637 ft. in Cook Mountain shale. After numerous tests the well was completed on Apr. 20, 1942, in a Yegua sand at 7919 to 7924 ft. for 54 bbl. of 52' gravity oil and 3,335,000 cu. ft. of gas through

Jan 1, 1943

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (-=,6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By S. Leber, R. F. Hehemann

Diffusion coefficients for the Cb-W system were measured using couples prepared from poly crystalline, commercially pure metals. The diffusion coefficients, measured in the temperature range between 1700° and 2300°C, decreased exponentially as the tungsten concentration was increased from 0 to 50 at. pct, then decreased abruptly at higher concentrations. A decrease of two orders of magnitude was observed over the entin? compositional range. The diffusion coefficients were in the range defined by the self-difiusion coefficients of the individual elements, indicating their general validity. An activation energy of 60,500 cal per mole was measured for the 20 pct W composition. Such low values, when compared with energies over 100,000 cal per mole for the pure constituent elements, indicated that transport mechanisnzs more rapid than volume diffusion were contributing substantially to inter dijfusion. Difference should, therefore, be expected between these data and the intrinsic diffusion coefficients. These differences should be significant in the kinetics of 'transport phenomena in practical systems. CONSIDERABLE attention has been devoted in recent years to the mechanical behavior and other properties of the refractory metals and their alloys. The Cb-W system has been of special interest as a base for the development of more complex compositions of commercial interest. In spite of the importance of mass transport to all aspects of elevated-temperature behavior, and especially to the production of alloys by powder-metallurgy techniques, little attention has been paid to diffusion in the Cb-W system. Results from a previous study of this system1 appeared to be anomalously high. The present investigation is, therefore, an attempt to obtain more accurate diffusion coefficients in this system. Intrinsic diffusion coefficients, of primary importance from the theoretical viewpoint, can only be obtained accurately from studies utilizing compositional gradients approaching zero. However, many practical problems involve diffusion under significant concentration gradients. The diffusion coefficients determined in this investigation were, therefore, obtained from couples prepared from elemental metals. The data obtained should be of value in the analysis of problems such as homogenization during powder-metallurgy alloying or reactions between base and clad in coated structures. In this vein, the investigation was conducted on poly crystalline materials of commercial purity. PROCEDURE Diffusion couples were prepared by sandwiching a columbium sheet between two sheets of tungsten. The composite was welded around all edges, the tungsten forming a protective can for the columbium. The composite was soaked for 4 min at 1600°C in a hydrogen-atmosphere furnace, quickly forged to 40 pct reduction in thickness, and then rapidly cooled to room tempera-

Jan 1, 1967

By Will H. Coghill, P. H. Delano, G. D. Coe

Data concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as " grindability-index numbers," but grind-ability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pull'erized product by a method comparabLe with- commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulvcrizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation,it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-¾-inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horsepower-hours." The channel-roller pulverizer hereinafter described is believed to meet these requirements. History oF the Machine The, work started when Ralph W. smith, engineer, St. Genevieve Lime Co., St. Cenevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasive-ness of dentifrices,1 and it was thought the same principles might be applied to coal, Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By R. I. Parsons, M. B. Standing, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By K. L. Sutherland, J. Rogers

The relationships between collector and mineral, activator and mineral, and activator, collector and mineral will be considered herein. We propose to criticize current theories of flotation but we will not repeat the many pertinent arguments presented by Wark and Cox28 in 1937 in which the "chemical" or more strictly the "solubility" theory proposed by Taggart and co-workers22 is shown to be untenable. Recently Taggart, Arbiter and Kellogg24 have studied the long-chain aliphatic amines as collectors and have attempted to resuscitate the solubility theory for these particular collectors. Dean and Ambrose3 have felt that "we stumble over words" when we distinguish different mechanisms of adsorption. Our view is that nothing is more stultifying to the development of a science than attempts to force widely different phenomena into one classification. This oversimplification leads immediately to difficulties in the interpretation of results. Experimental Procedure The response of minerals to activator and collector was determined by "captive-bubble" tests. The methods of preparation of specimens26 and of testingin have been previously described. Results from captive-bubble tests were confirmed by flotation tests in glass-stoppered cylinders.26 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±o.2 pH units and ±5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible by a cross and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, the experimental results being indicated on the figures by a square. The curves show the limits of composition of solution in which flotation in a cell would be possible. Many factors other than those considered in these tests determine recovery or grade of a given mineral in practice.

Jan 1, 1947

By S. C. Sun, A. M. Gaudin

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by Pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (=10-6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By J. M. Schopt

COAL petrology is the study of the lithologic composition and texture of coal and includes megascopic as well as microscopic differentiation. Coal petrography is a quantitative study, principally (but not exclusively) microscopical in nature. The distinction between coal petrologic and coal petro-graphic studies usually is not important, but it is important to recognize that these studies differ materially from other types of petrology that deal primarily with minerals. The petrologic entities* of coal are less clearly distinguished than most minerals and the basis of distinction is not always clearly expressed. The relation of coal petrology to geologic, mining, and technologic problems is most evident when results of coal petrologic studies can be stated quantitatively. The chemical and physical composition of coal and the determination of its quality and properties are continuing problems. The source of these problems lies in the heterogeneity of coal and in its almost complete insolubility in ordinary solvents at normal temperatures. The empirical and comparative character of standard chemical coal analytic values is one of the consequences resulting from heterogeneity and insolubility of coal. Nevertheless, these coal analytic methods are highly technical and diversified. Coal petrol.ogy employs a group of similar analytical methods which provide information about coal that the other methods cannot supply. The heterogeneity of coal is most clearly demonstrated by means of petrologic studies. The properties utilized in coal petrologic studies are related to texture (size, form, and association), hardness, light reflectance, and light absorption and transmission (color). Size relations are most evident but are commonly overlooked. Coal is classed chemically as a mixture, and chemical analyses thus show the composition of the sample as a whole. Geologically coal is an organic clastic deposit, derived from diverse plant fragments and particles having a size range comparable to that of a conglomerate or breccia. The mixture of different materials that compose coal, large and small, can be realized only by microscopic study. This is because the fundamental cellular units of plants, from which coal is formed, are microscopic in size. The kinds of altered plant particles and fragments in coal have specific differences in hardness, reflectance, and color that signify differences in composition. These differences must be taken into account in evaluating the aggregate properties of coal. Terminology and Texture Full discussion of terms applied by various petro-logists in analysis of coal is beyond the scope of this article. For convenience the simpler types of petrologic entities that are defined without reference to lithologic occurrence or texture will be called coal components. Fig. 1 lists reactive and relatively inert

Jan 1, 1957

By R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-C and Fe-Ni solid-solution alloys has been investigated at 25°C. It is found that the rate of solid-solution strengthening is dependent upon the strain at which the yield stress is measured, the macroyield stress being much more concentration-dependent than the microyield stress. In fact the addition of nickel does not lead to any increase in the microyield stress of iron. The primary effect of increasing the carbon or nickel content is to increase the slope of the stress-strain curve in the microyield region; this effect has been correlated, by means of transmission electron microscopy, with a decreased ability of the dislocations to cross-slip. It is concluded that the Mott-Nabarro theory is a good description of true solid-solution hardening in these and other iron-base alloys. A.LL theories of the solid-solution strengthening1-4 indicate that the flow stress of an alloy increases both with solute concentration and "misfit" between the solvent and solute atoms. The functional relationship between strength, solute concentration, C, and misfit depends upon the particular theory. Mott and Nabarro1,2 and Schoeck and Seeger3 both predict a linear increase in strength with concentration, while Fleischer4 indicates that the strength should be proportional to C1/2; there are in the literature experimental observations to support both these compositional dependencies.1'8 The experimental evidence used to support the theories is the change in macroscopic yield stress (strain, e, = 10-3) with composition. However, recent investigations have revealed that solid-solution strengthening in a Cu-Al single crystals7 and in Fe-V polycrystal-line" alloys depends upon the strain at which the flow stress is measured; a flow stress in the microplastic range (e = 10-6 to 10-5) is much less concentration-dependent than the macroyield stress. Since the theories of solid-solution strengthening are concerned in particular with the stress to move a dislocation in a dislocation-free matrix, they should only be compared with microyield-stress data; it will be shown that in a material deforming homogeneously the microyield stress (e = 10-6) is approximately the stress to move through the matrix those dislocations which have been nucleated by stress concentrations such as particles or grain boundary ledges.9-11 In contrast, the macro-yield stress is more complex in that it is affected by several phenomena: dislocation multiplication, dislocation interactions, and the ease of propagating slip across grain boundaries. For example, it is experimentally observed that when long-range order12'13 or solute effects10 restrict cross alip the grain boundary

Jan 1, 1967