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By F. Weinberg

INTEREST is currently being directed toward grain boundary morphologies in zinc in terms of grain boundary facetingl and grain boundary energies.' Some years ago the present author attempted to measure grain boundary energies in 99.999 pct purity Zn as a function of boundary angle, using the standard procedure of measuring equilibrium angles of the boundary traces at triple points. This followed an investigation he carried out on preferential melting of |H (112) Fig. 1—Electron transmission micrograph of a stacking fault, grain boundary intersection in copper. GRAIN BOUNDARY STACKING FAULT Fig. 2—Schematic representation of the intersection of Fig. 1, indicating inclination angles 0 and trace angles $. specimens were prepared by the Bollman technique in an electrolyte of 70 pct methanol, 30 pct HNO3 main-tained at -30°C. The interfacial free energy of the high angle grain boundary and of the stacking fault is assumed to be thermodynamically equivalent to the corresponding in-terfacial tensions. In terms of the true dihedral angles & between the intersecting interfaces, the equilibrium of interfacial tensions in the direction parallel to the stacking fault yields: ysF = -ygb(cos F1+ cos ±cosF2) Here, ysF is the stacking fault free energy and ygb is the grain boundary free energy, assumed equal on both sides of the intersection. Forces acting normal to the grain boundary, of the form ??gb/?F,l are assumed negligible as the grain boundary remains straight for a considerable distance on either side of the intersection. The micrograph of Fig. 1 may actually consist of several closely spaced stacking faults on the same slip plane. The actual point of intersection between the grain boundary and the first stacking fault, and the equilibrium configuration of the intersection, should not be affected by the presence of the other faults, as

Jan 1, 1970

By A. E. H. Bergmann

INTRODUCTION The Sachtleben Chemie GmbH in Duisburg, a subsidiary of the Metallgesellschaft AG, operates a new sulfuric acid plant that employs fluid bed roasting of pyrite concentrates. The plant produces about 300,000 tons per year of pyrite cinders from the fluid bed roasting unit. The cinder product consists of 58 percent iron and is about 80 percent by weight smaller than 50 microns. This cinder product was found to be a competitive source material for the cement industry as the iron-containing additive. However, the extreme fineness of the cinder and its dusting tendency were undesirable and an agglomerating technique became necessary. In order to keep the price of agglomerated pyrite-cinders at a competitive level, the agglomerating method must be chosen such a way the capital and operating costs are low. Initial experiments were carried out on a laboratory scale to make an appropriate choice of the agglomerating method. Major goals of agglomerating the cinders were to improve the transportation, storage, and proportioning and metering properties. Minimum specifications are put on the size, size distribution and shape of the product. Criterion for handling is that a minimum of minus one mm. fines are produced after several handlings, while for storage, it is also desirable for the agglomerated product to survive several months in open air. Thermal agglomeration processes such as sintering one known to produce excellent products, but are by far too expensive for our application. For the same reason, granulation, balling, and pelletizing tests with addition of organic binding agents, such as tylose, starch, sulfite wash, molasses, etc. were not continued. The costs for the binding agent was considerable, which is probably due to the high pore volume of our cinders (35 %). Furthermore, the pellets or granules

Jan 1, 1977

W. ROWLAND Cox,* New York, N. Y. (written discussion?).-The process described by Mr. Malcolmson undoubtedly represents a great stride toward conservation of our natural resources. Without discussing the subject from an economic standpoint, I wish further to emphasize the fundamental principles of the Smith process in order that its economic value may be fully appreciated. The process is essentially a means of producing an ideal fuel, as regards its combustion qualities, by the removal of the so-called volatile matter from the coal, in the form of byproducts, which have value for other purposes far in excess of their fuel value. In other words, coals which contain. large amounts of gas, tar, and ammonia, and are not suitable for domestic or industrial fuel, or for treatment in byproduct coke ovens or gas retorts; because they possess poor coking qualities, can he prepared for commercial use by the. Smith process with a very high degree of efficiency. Much work has been done along this line, both in this country and in Europe, in developing a means of preparing coal, as the economic advantages have long been recognized. To the best of my knowledge, the Smith process is the only one that has proved its commercial adaptability. Distillation of coal at 900° to 1000° F. (480° to 540° C.) yields a large amount of tar and oils. The residue of the distillation, however, is a very friable semi-coke, wholly unsuitable for use as a fuel, unless it can be charged directly into a byproduct gas producer. The problem which confronted the inventor was then to convert this carbon residue into a commercial product, and it is in this step that the Smith process has overcome the obstacles which prevented a number of other methods from becoming commercially practicable.

Jan 10, 1918

Discussion -of the paper of I. N. KNAPP, presented at the New York meeting, February, 1915, and printed in Bulletin No. 96, December, 1914, pp. 2783 to 2793. A. C. LANE, Tufts College, Mass.-Is there any noticeable effect in drilling against salt water? Mr. Knapp says that the mud settles very quickly when brine is added-. What is the effect when you strike a strong salt water ill boring? I. N. KNAPP.-You are supposed to have enough mud pressure in your well to keep the saltwater out. I have drilled against what I knew to be 80 ft. head of water, and hot water too at 99.5°; this water did not show until the well was bailed and the mud pressure reduced. HENRY Louis, Newcastle-upon-Tyne, England (communication to the Secretary*).-Mr. Knapp may be interested to learn that the use of mud in drilling through porous strata is much older than lie appears to be aware of. It has been used notably by Honigmann for boring shafts in Holland and in some of the adjoining portions of Germany. At the Oranien Nassau colliery, shafts about 12 ft. in diameter and 425 ft. deep were sunk in. this way-namely, by boring with a rotary borer, a thick mud puddle being pumped into the shaft, so as to maintain a pressure in the shaft greater than the hydrostatic pressure in the surrounding loose sands and thus keeping the sides of the shaft from collapsing. He will find references to this method in Das Abbohren von Schächten; Handbuch der Ingenieurwissenshaften, p. 134, also in the Transactions of the Institution of Mining Engineers, vol. xiii (1896-97), p. 155. The process appears to have been employed even before 1895, though I cannot give the exact date when it was first used.

Jan 5, 1915

By E. J. Dulis, V. K. Chandhok, J. P. Hirth

Cobalt clearly increased the activity of carbon in austenite and in ferrite. This effect of cobalt on carbon activity Plausibly accounted for the effect of cobalt on accelerating the austenite to pearlite transformation. Cobalt was found to have only a slight effect on carbon diffisivity in various Fe-Co and Fe-Co-W-Mo austenites, but was found to decrease carbon diffusivity in Fe-Co ferrite. THE effect of cobalt in steel is unique in that it is the only element that reduces hardenability by accelerating the austenite to pearlite reaction. The results of several excellent investigations aimed at explaining the role of cobalt have been published,1"7 but a complete understanding is still lacking. In addition, cobalt significantly enhances the resistance to softening or tempering of highly alloyed highspeed and hot-work tool steels. The resistance to tempering is related to the secondary hardening reactions associated with the fourth stage of tempering during which carbides of molybdenum, tungsten, and/or vanadium form in a martensite matrix. The effect of cobalt on secondary hardening reactions in high-alloy tool steel has received considerable attention, but a full explanation of the reactions involved has not been developed. Inasmuch as austenite to pearlite transformation and secondary hardening involve carbide formation, the present authors believed that the role of cobalt in effecting carbon activity and diffusivity in austenite and in ferrite was important to a fuller understanding of the phenomena involved. TO investigate the effect of cobalt on the activity coefficient of carbon in austenite, an approach was used similar to that used by Darken17 in his experiments on the effect of silicon, manganese, and molybdenum on carbon activity and diffusivity in austenite. TO

Jan 1, 1962

A PAPER on "Iron and Steel Scrap in Blast-fur-nace Burdens," by W. C. McKee, general super-intendent, Federal Furnace plant, By-Products Coke Corp., Chicago, was published in the October issue of MINING AND METALLURGY, and written discussion by Richard Moldenke was published in the December issue. Following is the stenographic report of the oral discus-sion that took place when this paper was presented at Pittsburgh. J. N. REESE, Monessen, Pa.-I came to the conclusion that Mr. McKee must be using a poor grade of scrap, therefore his loss was high. Mr. Franchot said that there was ex-cess heat in the stack. There is no excess heat in the hearth, therefore, any heat that is used to melt this scrap must come from the stack. By using scrap in a blast furnace you can utilize this excess heat in the stack. The amount of scrap that can be used in any particular furnace involves a direct relation to the efficiency of that furnace. If a furnace is running on a very low-coke rate, you will not be able to use much; if on a high-coke rate, you can use considerable scrap, probably several times as much as that mentioned in these papers-without using any additional coke. This excess heat can be utilized with-out practically any serious mechanical and operating diffi-culties such as might be occasioned by removing gas from a point other than the top of the furnace. I do not think, scrap has any effect on the iron, although I think some foundrymen are trying to prove that it has, and perhaps some open-hearth men may have that idea.

Jan 1, 1927

By J. C. Jaeger

It frequently happens in engineering and mining situations that "bad" rock is encountered which consists of rock broken up into blocks a few inches or less in diameter by a network of intersecting joints. These joints may be open, or filled by veins of solid material, or covered with weathering products. Essentially, the material consists of an aggregate of small interlocking blocks. In such circumstances, major joint systems usually can be recognised and studied, but there are probably many minor planes of weakness which may cause the blocks to be of almost random shape. It is extremely difficult to determine the properties of such materials. Measurements on small specimens give the properties of the constituent rock and not the jointed material. At the other extreme, the material has occasionally been tested as loose aggregate in large triaxial pots, but this gives no information about the strengthening effect of the interlocking of the small blocks of rock. One simple approach, which has been much used, is to regard the rock as randomly jointed on a small scale and to apply soil mechanics theory to it. In this case, the normal and shear stress at failure are related by [ ] where the coefficient of friction p and the cohesion c will be those of the individual joints. Even in very bad rock, it is usually possible to drill core in small diameters of 1 to 2 in. which will contain a number of joints, both open and filled. The testing of such joints provides one simple method of determining some of the properties of closely jointed rock and will be discussed in detail in the next section. Calculations based on Eg. 1 with values of c and µ obtained in this way may be expected to give a lower limit for the strength of structures in rock.

Jan 1, 1970

By F. F. Craig

The authors have done a commendable job in combining a number of recognized waterflood performance prediction methods into one composite method. The availability of a FORTRAN program for this composite method should encourage its widespread industry use. Pan American has had a computer program developed along similar lines for a number of years,' and it has received more use than any other reservoir prediction method. In three important stages of a pattern waterflood, the authors fail to consider fully the effects of water-oil mobility ratio on performance. This is discussed in the following paragraphs and modifications of the prediction method are suggested. During the early stages of a waterflood in a partially depleted formation, the injected water and its preceding oil bank move out radially from the injection wells. As pointed out in the author's paper the method of Yuster and Calhoun2 or predicting the water injection rate during this period assumes that the mobilities of the water and oil are equal. In his book, Muskat3 resents a modification of the Yuster-Calhoun approach that considers fully the influence of water-oil mobility ratio. In Muskat's method, the prediction of the injection rate-injected volume-time relationship is expressed in readily programmed dimension-less unts. At and following fillup the five-spot pattern consists of a water-invaded pattern with the remainder of the pattern containing only oil and connate water. In the paper, Eq. 18 is used to calculate the water injection rate at fillup. This equation considers that the entire pattern is invaded by water. To properly consider both the incomplete areal sweep of water and the water-oil mobility ratio, Eq. 18 should read:

Jan 1, 1969

By K. Heindlhofer

ESTIMATES of the "plasticity" of a metal are commonly deduced from three types of test-tensile, torsion and impact. The several results have been more or less at variance, though this disparity has attracted little notice, largely perhaps because they have been expressed in different terms. The discrepancy between the results of the three tests becomes obvious when each is made at a series of low temperatures, for the temperature range within which the "plasticity" of iron largely disappears proves to be very different in the three types of test. The rather abrupt disappearance of "plasticity" of iron within a narrow temperature range cannot be due to any physicochemical change (such as a precipitation) taking place in the material at that time, because the original plasticity is immediately regained when the temperature of the material is brought above the sensitive range. Accordingly this differ-ence in behavior shows that the "plasticity" of a metal depends upon the mode of action of the stresses which produce the deformation, and there-fore upon the method of test. Analysis of the stresses leads to the conclusion that the observed plasticity of a metal is determined by the relation between its resistance to rupture by separation and its resistance to shear (slip), on the one hand, and between the effective normal and shearing stresses on the other; and that the relation between the two resistances does not in general remain constant with change of temperature, and may somehow be altered to some extent by the previous treatment of the specimen. This suggests the view that the results of none of the usual mechanical tests are directly comparable even for a single metal tested at a series of tem-peratures, or for a series of metals at one temperature, because the propor-tion of the total resistance of the metal to the test contributed by the

Jan 1, 1934

By J. W. Rutter, K. T. Aust

Competitive growth of recrystallized grains into striated single crystals of zone-refined lead produced preferred orientations of the coincidence type after annealing at 175°C, but not at 300°C. This preferred orientation development was found to result from the higher mobility and lower energy of large -angle coincidence boundaries compared to large-angle noncoincidence boundaries. These mobility and energy difference provide a useful basis for explaining many cases of preferred orientation observed in annealed metals. DURING a study1 of the mobility of grain boundaries in zone refined lead, it was observed that the temperature dependence of the grain boundary migration rate is smaller for large-angle, coincidence-type grain boundaries than for large-angle noncoincidence ("random") boundaries. This observation is illustrated schematically in Fig. 1, which shows log rate of grain boundary migration vs reciprocal absolute temperature for two large-angle boundaries. The upper curve refers to a coincidence-type boundary of the sort discussed by Kronberg and Wilson.2 While the mobilities of these two boundaries are similar at 300°C, the coincidence-type boundary has a greater mobility, by a factor of about: four, at 175°C than does the noncoincidence boundary illustrated in the lower curve. The observation described above suggested a simple experiment for testing the role of grain boundary mobility in the development of preferred orientation in annealed, high-purity lead. On the basis of this observation, it would be expected that if a large number of grains of different orientations are growing competitively, and if relative grain boundary mobility is a controlling factor, then the specimen procluced by boundary migration will contain crystals having random orientations if annealing is done at 300°C, while preferred orientations of

Jan 1, 1962

By Charles A. Ashburner

The petroleum industry of western Pennsylvania and southwestern New York lias been one of phenomenal development. Greater and more sudden flucuations hare occurred in the price* of crude oil, and in all the collateral interests dependent upon its production, than in the case of any other mineral product which has been extensively exploited in the United States. This was more particularly so from the commencement of drilling for oil in 1859 down to the end of 1877. The experience gained during these early years has enabled the oil men to operate more intelligently since; the business is not now attended with the hazardous risks with which it is generally credited. The most important questions connected with the oil industry are those of (a) the oil-supply, and (6) the possible ultimate exhaustion of the field. Since 1876 my attention has been directed to the study of the statistics of the product of the oil regions. In January, 1880, in order to slow some interesting points connected with these questions, I prepared a graphic chart which was used to illustrate a lecture on petroleum delivered before the Franklin Institute. This chart was afterwards reconstructed in two distinct forms for publication in the census report. on Petroleum and its Products. These latter I have redrawn in a condensed form, and have extended them to include the statistics up to 1885, for publication in the Transac tions of the Institute, in conjuction with a map of the oil-re&'~IOIIS prepared by Mr. John F. CarII and myself. It is hoped that these illustrations will be found interesting to the members of the Institute, and of practical utility to oil-men, without any extended discussion, since it is my desire to make only such brief references to them and give such additional detailed facts as may serve to make the prominent features understood.

Jan 1, 1886

By Harold L. Bare, Frank R. Barnako

Coal mining historically has been a. hazardous occupation but, in recent years, tremendous progress has been made in reducing accidental coal mine deaths and injuries. The purpose of this chapter is to discuss the basic principles of accident prevention as they are related to coal mining. Accident prevention fundamentals are no different for coal mining than for any other type of work. The fundamentals apply to all industries. Construction workers may be struck by falling tools and materials, and miners may be struck by falling slate and coal. Sailors may be trapped by shipboard fires, and miners may be trapped by mine fires. Railroad brakemen may lose hands and fingers positioning couplers, and miners may lose hands and fingers positioning couplers. Many other examples could be cited, but the point is that accidents that happen in coal mines are basically similar to accidents that happen in other industries. Thus, the basic principles for preventing accidents apply in coal mining as they do in any other type of work. COAL MINE ACCIDENT EXPERIENCE The US Mine Safety and Health Administration (MSHA) is the main source for accident experience data in coal mines. Coal mine operators are required, by law, to forward to MSHA monthly the number of fatal and disabling injuries, man-hours worked, and tons of coal mined. This information is compiled and published quarterly, with annual summaries, by MSHA. Trends in the number of fatalities and fatal injury rates are shown in Fig. 1. Major coal mine disasters, with number of miners killed, and dates of coal mine safety legislation are shown in Table 1. The fatal and disabling injury frequency rates for the coal industry are shown in Fig. 2.

Jan 1, 1981

By Dr. O’Neil Thomas J., Donald W. Gentry

"October. This is one of the peculiarly dangerous months to speculate in stocks. The others are July, January, September, April, November, May, March, June, December, August and February." -Mark Twain Although the preceding chapters describe the type of preliminary evaluation frequently performed in the mining industry, it has been assumed that input data are known with certainty-clearly an enormous simplification. In reality, estimates of ore grade, mining cost, metal price, etc., are subject to varying degrees of uncertainty due to the inability to predict the future with much precision. Management would probably not, for example, be equally attracted to two projects each offering a 20% DCFROI-one for a new gold venture in Nevada and the other for an undersea manganese nodule operation in the Pacific. The high risk with the latter investment tells the obvious; there is more to investment decision-making than a deterministic analysis using "best estimates" of input parameters. The science of decision theory normally distinguishes between decisions under uncertainty, where probabilities of various outcomes are unknown; and decisions under risk, where such probabilities can be estimated. The first case is rarely en- countered in practical capital investment analysis in mining, so the remainder of this chapter focuses on that class of problems where rational probability distributions for the future states of input variables can be estimated. RISK IN MINING Risk in the context of this chapter is the unforeseen deviation of individual cash flows from expected values for a capital project. For a mining venture, the source of this uncertainty could be any number of factors relating to such items as ore grade, ore reserve tonnage, operating costs, product prices, etc. With conventional *Adapted from O'Neil, T.J., 1979, "Procedures for the Preliminary Financial Evaluation of Metal Mining Ventures," Computer Methods for the 80s, A. Weiss, ed., AIME, New York, pp. 556-573.

Jan 1, 1984

By Clare B. Carlson, C. P. Proctor

THE history of the froth flotation of coal is relatively short. The flotation process was applied to fine-coal cleaning about the time of the end of World War I. Coal flotation finds more widespread use in Europe than in the United States and is used on a commercial scale in nearly all major coal-producing countries in the world. In Fig. 1 the general arrangement of a froth-flotation plant at a British colliery is shown. GENERAL FEATIJIEES OF THE PROCESS Application The flotation process is applicable to the cleaning of the fine sizes, particularly minus 48-mesh coal, although it may be used on sizes as coarse as 1/8 in. Since most cleaning processes usually are not effective on sizes smaller than 48-mesh and certainly not effective on minus 100- mesh, the froth-flotation process offers a solution to the problem of cleaning these sizes. This process consists-of agitating the feed pulp with a small amount of reagents, usually 1.0 to 2 ½ lb. per ton of feed in the presence of water and air; the reagents help to form small bubbles that collect on the particles having a greater affinity for the bubble surface than for the water surface, in this case the fine coal, and the bubbles buoy these particles to the surface to form the frothor concentrate. Slate and shale particles remain wetted and suspended in the water to be drawn off as tailing. The frothers commonly used in coal flotation are cresylic acid, pine oil, and alcohols. More expensive frothers, used in ore flotation, work satisfactorily but do not compare with these cheaper reagents for over-all cost. Collectors- used are low-grade petroleum fractions, such as cheap, partly refined fuel oil, or lubricating oil, sometimes mixed with small amounts of kerosene. Other collectors used are the fatty acids and their

Jan 1, 1943

By P. W. Ramsey, D. P. Kedzie

INCREASING demand for improved strength-weight ratios made on aircraft structures has resulted in a gradual increase in the tensile strength requirements for steels used in such applications. As the cyclic loads often are more critical than static loads, and the fatigue properties are generally the design criteria, the question arises as to whether an improvement in fatigue properties accompanies the increased tensile strength. The present investigation was undertaken to determine the relationship between fatigue and tensile properties for an aircraft quality steel in the 155 to 280 ksi (1000 psi) tensile strength range, using the Prot method of fatigue testing. Procedure and Results After preliminary work to establish proper heat treating procedures for this heat of aircraft quality electric furnace steel (a Ni-Cr-Mo-V steel," AMS- Prot Fatigue Testing Method—The determination of the endurance limit by the conventional Wohler method can be time-consuming and easily require 20 specimens when statistical variance is to be established. This is also true when endurance limit loads are determined on actual parts or subassem-blies, and the desirability of a reliable accelerated method has been evident for some time. The primary advantage of the Prot method of fatigue testing is in reducing the number of specimens and the time required for each test. Unlike the Wohler method, every Prot specimen tested con- tributes to the determination of the endurance limit, and the authors have been able to duplicate Wohler results obtained with 20 specimens with only half the specimens and a fourth of the total cycles. This new technique for defining the endurance limit was proposed in 1948' by Marcel Prot and consists of progressively increasing cyclic stress until fatigue failure occurs. By varying the load rate, a, a useful relationship is found to exist with failure stress, so that for steel the failure stress appears to

Jan 1, 1958

"The Midvale. Plant of the United States Smelting, Refining and Mining Company, situated twelve miles south of Salt Lake City, consists of mills for concentrating lead-zinc ores and a custom lead smelter.The milling department includes a 475-ton gravity mill for ores from the United States Mines at Bingham, a 100-ton Huff electrostatic zinc plant and a 60-ton pilot flotation mill for differential separation of lead and zinc. The gravity mill and electro¬static plant are being replaced by a 600-ton differential flotation plant, now under con¬struction, for differential separation of lead, zinc and iron. This new mill will have cap¬acity for treating custom ores in addition to ores from the company's mines at Bingham.The smelting department is equipped to handle 1600 tons of charge per day through six blast furnaces, 48 inches by 160 inches at the tuyeres. All gases from both blast furnaces and roasters are filtered through baghouses, which remove the dust from the gases so effectively that even when the plant is running at full capacity no smoke can be seen coming out of the 450-foot brick stack handling rca2ter gases, nor out of the two shorter steel stacks which take the blast furnace gases. On this account the Midvale plant has come to be known as the ""smokeless smelter.""The blast furnace gases are filtered through 832 woolen bags, 33 feet 6 inches by 18 inches in diameter, and 1200 woolen bags, 28 feet by 12 inches in diameter."

Jan 1, 1925

By Edward Steidle

It has been said that "the command of nature has been put into the hands of man before he knows how to command himself," and what we see about us gives particular emphasis to this observation. If this condition be granted, the vaunted boast of school and college, of the institution that had the training of this generation, and of its fathers, and of its grandfathers, the boast that education is a "preparation for life," stands exposed as a hollow claim, or as a ghastly, cynical conception of life, or else education has fallen far short of its intentions. It has been evident for some time that education was not meeting the fullest expectations of society. In recent years there has been a deal of speculation indulged in by both laity and faculty in regard to American education and American civilization, and some few and sporadic changes have been effected. Today, however, there is no longer time for mere hypothetical considerations; we are faced with certain definite facts and confronted with obvious conditions that will not wait for fine-spun theories. If educators do not put their house in order, someone else will do it for them. The trends in mineral industries education must be in harmony with this general realignment that is today visible on the educational horizon, and only as these trends are in conformity with this movement can they be called sound. Two questions, then, confront mineral industries educators: (1) What are the trends in mineral industries education, and (2) how do these trends correlate with the major educational movements of the day? Scope or Mineral Industries Education Before launching into these particulars, it might be well to define the scope of mineral industries education and to consider its present position. Mineral industries education embraces three main types of work: 1. Earth Sciences and Geography.—Geology, mineralogy, geography— courses basic to all mineral industries and to the humanities. 2. Mineral Engineering.—Mining, petroleum and natural gas—dealing with mineral producing industries. Application of earth sciences and all types of engineering to exploitation of natural mineral resources.

Jan 1, 1934

By W. O. Philbrook. K M Goldman, M. M. Helzel

RADIOACTIVE calcium has been used to learn whether calcium can be detected in iron saturated with carbon after it has been melted under CaO- A12O3- SiO2 slags similar to those used in the iron blast furnace. It was hoped that the radioactive tracer technique might make possible a general study of steelmaking reactions in which calcium or calcium oxide are involved. No calcium could be found in the metal under conditions which were favorable for the reduction of calcium, and it has been concluded that the calcium content of the iron was less than 6 x 10 - pct. Some of the problems encountered have been instructive with regard to pitfalls and limitations of tracer methods. Calcium oxide occurs in almost all iron- and steelmaking slags, and it is essential to the success of all commercial basic steelmaking processes. Calcium alloys are sometimes used in the deoxidation of steel and for the innoculation of gray iron. The element calcium is therefore almost as ubiquitous in the steel industry as are carbon and oxygen, but calcium has been thought to be completely immiscible with iron in both the liquid and the solid states.' It does not seem entirely unreasonable to Suppose, however, that some low concentration of calcium might exist in liquid iron under a basic slag with other conditions being favorable, just as silicon and other elements can be introduced into iron by reduction of their oxides from slags under appropriate circumstances. The radioactive tracer technique offered a more sensitive method than chemical analysis of testing this supposition. The reasons for interest in this investigation were strong enough to justify a recognized risk of failure. On the theoretical side, information on the distribution of calcium between liquid iron and a slag and the rate at which the equilibrium distribution is approached would contribute strongly to the general theory of slag-metal interface reactions. Furthermore, any evidence on the presence of calcium in liquid iron might provide a vital clue to the mechanism of the desulphurization of iron by slags. All of the reactions which have been proposed to explain desulphurization postulate that the sulphur ultimately becomes fixed in the slag as calcium sulphide, but the mechanism by which sulphur

Jan 1, 1951

By C. S. Giggins, F. S. Pettit

The oxidation properties of Ni-Cr alloys with fine grains, coarse grains, and deformed surface layers have been studied at temperatures of 900" and 1100°C in 0.1 atm of oxygen. The oxidation rates of alloys containing between 10 and 30 wt pct Cr have been found to be dependent upon the grain size of the alloy. Finegrained alloys had smaller oxidation rates than coarsegvained alloys because of the selective oxidation of chromium at alloy grain boundaries. In this compositional range alloys with deformed surface layers behaved similar to fine-grained alloys due to recrys-tallization of the deformed surface layer. In the preceding paper1 it was found that during the oxidation of Ni-Cr alloys, the volume fraction of precipitated Cr2O3 could be greater at alloy grain boundaries than at other areas of the alloy surface. In the case of alloys with chromium concentrations equal to or greater than 30 pct,* the volume fraction of Cr2O3 *AIL compositions are given as weight percent unless specified otherwise. precipitated at grain boundaries and within grains on the alloy surface both exceeded the critical amount required for lateral growth of the Cr2O3 particles and the surfaces of these alloys were completely covered with a continuous, external layer of Cr203 during oxidation. However, in the case of alloys with chromium concentrations between approximately 5 to 30 pct, the volume fraction of precipitated Cr2O3 exceeded the critical value required for external scale formation only at grain boundaries.but not within the interior of the grains. Consequently, the surfaces of these alloys had external scales of Cr3O3 over the grain boundaries but internal Cr2O3 subscales with external scales of NiO away from the grain boundaries. Under these latter conditions, it was found that chromium could diffuse laterally in the alloy from those areas covered with an external layer of Cr2O3, i.e., grain boundaries, to areas where the Cr2O3 was present as a subscale. This diffusion of chromium resulted in an increase in the volume fraction of Cr2O3 precipitated in the sub-scale zone and continuous layers of Cr2O3 could be formed at the subscale front in these regions. For the alloys used in the previous studies,' continuous layers of Cr2O3 were formed on Ni-20Cr alloys in the subscale regions after approximately 30 hr of oxidation at 900°C. For shorter periods of oxidation, the Cr2O3 layer was semicontinuous with the continuous portion at the subscale front emanating from points where the Cr2O3 had been formed as an external scale over alloy grain boundaries. Some lateral growth of a Cr2O3 layer in the subscale region was observed on Ni-15Cr and even Ni-10Cr alloys but this layer was never continuous after 30 hr of oxidation. These results indicate that the selective oxidation of chromium in Ni-Cr alloys with chromium contents between 5 to 30 pct may be dependent upon the grain size of the alloy. Fine-grained specimens in this compositional range should have a larger fraction of the surface covered with external Cr2O3 than coarsegrained specimens and the subscale areas required to be sealed via lateral diffusion of chromium should be smaller. It is therefore to be expected that a continuous layer of Cr2O3 can be formed on alloys in this compositional range after short periods of oxidation providing the alloy grain-size is sufficiently small. bo studieS2,3 have established that the oxidation behavior of alloys can be significantly influenced by pretreatments which produce mechanically deformed surfaces. It has been found that deformed surfaces usually promote the selective oxidation of elements in alloys and it is believed that these effects are due to rapid diffusion of elements in the deformed layer. In view of the previous results,' which showed that alloy grain boundaries may play an important role in the selective oxidation of chromium in Ni-Cr alloys, deformed surfaces may promote the selective oxidation of elements in alloys as a result of the numerous grain boundaries formed on the alloy surfaces via recrys-tallization during heating to the oxidation temperature. The purpose of the present studies was to determine the effect of alloy grain size and surface deformation on the selective oxidation of chromium in Ni-Cr alloys at temperatures of 900" and 1100°C in 0.1 atm of oxygen. EXPERIMENTAL The average grain diameter of the alloys used in the previous studies1 was not less than 0.04 mm and alloys with compositions between 5 and 30 pct chromium had average grain diameters between 0.04 and 0.14 mm. Since the oxidation kinetics were already available for these relatively coarse-grained alloys, it was desirable to use these same alloys in the present studies. The surfaces of the alloys listed in Table I of the previous paper were deformed by using a Model F S.S. White Industrial Airbrasive Unit, which delivered a controlled mixture of 25 µ Al2O3 particles in a stream of dry air at high velocity against the surface of a specimen. The amount of surface deformation produced by this treatment was not determined but a re-crystallized layer about 15 µ thick was formed upon annealing deformed specimens. The grain size at the surface of the specimens was reduced to an average grain diameter of 0.01 mm by annealing the deformed specimens, i.e., grit-blasted,

Jan 1, 1970

By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,' who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.' In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.' This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.' However, to the best of the authors' knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956