Search Documents

By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months' furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957

By L. J. Dijkstra

During the past several years an extensive study has been made of the internal friction of iron containing carbon or nitrogen in solid solution.1,2,3,4,5 It has been found that a sharp peak is observed in a plot of the internal friction vs. temperature of measurement. With a frequency of about one cycle per second, this peak occurs at 20°C for N and 36°C for C. The physical origin of this anomalous internal friction was traced by Snoekl to the local tetragonal symmetry of the interstitial positions in body centered cubic (bcc) iron. A change in stress induces a change in the equilibrium distribution of the interstitial atoms among the three types of interstitial positions, the three types corresponding to the three directions along which the tetragonal axis may lie. It is the continual striving of the interstitial atoms to maintain an equilibrium distribution that gives rise to a phase lag between strain and stress during oscillation, and hence, to internal friction. A similar type of internal friction has been observed in the bcc lattice of tantalum containing in interstitial solid solution C, N or 06. The theory of this anomalous internal friction leads to the prediction that its magnitude is strictly proportional to the concentration of either the carbon or the nitrogen in solid solution, provided the concentrations are small. This prediction has been verified3 for the range of solubilities ohtainable in alpha iron. This proportionality provides us with a new tool for the study of nitrogen and carbon in alpha iron. It thus enables one directly to follow the precipitation of either of these solute atoms from solid solution and also directly to measure their solubility as a function of temperature. A preliminary study of precipitation using this method has already been presented by the author.3 The purpose of this paper is to present more extensive observations upon the precipitation of N and C in alpha iron, as well as to present observations upon the solubility of N and C in alpha iron which, at least in the lower tempera- ture range, are believed more accurate than those previously obtained by other methods. The interpretation of the observations upon precipitation involves the use of the appropriate equilibrium diagrams. For ease of future reference in this paper the equilibriunl diagrams for the Fe-N and Fe-C systems are accordingly reproduced as Fig 1 and 2, respective]y. Experimental Procedure The specimens were made of West-inghouse Puron iron and consisted of wires 0.025 in. in diam and about 1 ft long. By a wet hydrogen treatment the specimens were purified of C and N. In

Jan 1, 1950

By Sidney H. Haughton

WHEN the white pioneers of the eighteenth and nineteenth centuries advanced from the coastal settlements of southern Africa into the interior of the subcontinent, they found it inhabited, more or less sparsely, by brown or black peoples mainly of pastoral habits but equipped with a fighting spirit and certain fighting weapons. Some of the tribes were smiths, others were miners and metallurgists; all used fuel, either industrially or domestically. Some of that fuel was wood, some cattle dung, and in some places the natives mined outcrop coal. Coal was first discovered by Europeans in Natal about 1840. After proper deliberation and after allowing due time for a consideration of all the implications, the Natal Government decided in 1881 (40 years after) to import an English expert to investigate and report on the discovery. Things then moved rapidly, and in what to a geologist is the remarkably short space of eight years, Natal collieries were producing at the rate of nearly 30,000 long tons per annum or 100 long tons per working day!

Jan 1, 1945

IT IS impossible to speak in exact terms of the effect that selective flotation has had, is having, and may have on the State of Utah. Its results enter into the economic structure of the state in so many ways and its ramifications are so widespread, that every line of industry is affected. Some effects can be definitely determined; others can be reasonably approximated; but the effect as a whole can not be set out in exact figures. Utah is essentially a mining state; mining is its basic industry and always will be. Agriculture, equally a basic industry, and of course, equally vital, can be practiced on only 6 per cent. of the 85,000 square miles of its area. It follows, therefore, that the economic future of this state depends upon a development of its natural resources. About 6 or 7 years ago, the mining industry in Utah was at a low ebb. This condition was caused partly by postwar conditions and other temporary causes, but prevailed also, which was most important, because the direct-smelting ores of the state were being rapidly exhausted and the cost of treatment of complex ores was almost prohibitive. Furthermore, the wet concentration of low-grade ores was unsatisfactory and did not result in producing a good smelting product. On visualizing this situation, one of the large smelting companies in the valley had the courage, ability and faith to develop and expand the principles involved in selective flotation of complex ores. This example has been followed by other smelting and reduction companies and the result has changed the entire aspect of the mining industry in Utah. The utilization of the zinc in the low-grade, lead-zinc-silver ores was the principal problem to be solved. The average yearly production from the State of Utah for the 10 years beginning 1914 and ending 1923, was something less than 10,000 tons of zinc concentrates. This period includes the world war, when abnormal prices stimulated production. In 1924, selective flotation began to be practiced on a considerable scale, replacing concentration by gravity and bulk flotation which had been used generally until this time. PRODUCTION AND VALUE OF ZINC CONCENTRATES The production of zinc concentrates during 1924 was approximately , 24,000 tons, or twice the average yearly production of the previous 10

Jan 1, 1928

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1940 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. TECHNICAL PUBLICATIONS in Classes A-Metal Mining, B-Milling and Concen-tration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETRO-LEUM TECHNOLOGY, which was issued quarterly in 1940 but will be issued every other month in 1941. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysical Methods of Exploration are issued as separate pamphlets. An Institute member is entitled to one copy of any TECHNICAL PUBLICATION or CONTRIBUTION. Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute accord-ing to their registration by classes. CONTRIBUTIONS and other TECHNICAL PUBLICA-TIONS will be sent upon request. A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page; minimum charge, 25¢. Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1.25 domestic, $1.35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2.50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7.80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers). MINING TECHNOLOGY, $6 per annum domestic, $6.60 foreign (metal mining, milling and concentration, Industrial Minerals Divi-sion, and mining geology papers.) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6.60 foreign. Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY is mailed each month. A member is entitled to one volume a year on his membership and he may purchase for $2.50 one copy of a volume not already received; additional copies of the same volume, $5. Nonmembers may pur-chase the volumes listed, at $5 each, plus 60 cents for Canadian or foreign postage. Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 50¢ each to members; to nonmembers 506 current issue and $1 each, back issues. Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4.00 foreign.

Jan 1, 1940

For the seventh consecutive year, the value of nonfuel mineral raw ma¬terials produced in the US set a new record, reaching almost $20 billion-up 12.7% from the previous year, according to the US Bureau of Mines. The Bureau reported that this mineral production was the basis for about $200 billion worth of processed materials of mineral origin.

Jan 5, 1979

By Frederick Beckett

WIDESPREAD experimentation has been conducted in recent years to devise a means of preventing intergranular corrosion in austenitic chromium-nickel steels of the 18 per cent chromium-8 per cent nickel type. Additions of titanium to these steels have been used commercially to overcome this difficulty, as advocated by Krupp of Germany, and the latest literature reference concerning improved details of this method is the article by Bain, Aborn and Rutherford.1 Extensive work by the present authors has shown columbium also to be a particularly valuable agent for inhibiting intergranular corrosion. This paper does not deal with steels that are largely or wholly aus-tenitic ; it is limited to a discussion of the results obtained through the use of titanium and columbium in plain high-chromium steels. For many years titanium has been used commercially by some steelmakers as a cleanser, and to a lesser extent as a hardener, but then in greater per-centages. The results of the work to be described disclose that titanium and columbium in proper proportions act as effective softeners in the high-chromium steels. It is well known that chromium intensifies the hardening effect of carbon in steel; it imparts pronounced air-hardening properties within a rather wide range of chromium content; it provides increased ductility in steels of given strength and hardness; and it enhances resistance to corrosion and oxidation at elevated temperatures to a marked degree. However, in applications requiring a combination of some of these valu-able properties great hardness is frequently a detriment rather than a merit. When the objective is a soft and ductile steel having optimum corrosion resistance, the producer strives for a carbon content as low as commercially practicable.

Jan 1, 1933

By A. M. Gaudin

THE so-called Kick law' is generally accepted to . mean that for each reduction to one-half in particle diameter, in a unit weight, the same amount of work is required. In crushing-efficiency calculations on crushing tests it is customary, when basing the calculation on Kick's law, to assign ordinal numbers to each standard sieve size. These ordinal numbers increase by a constant difference with each successive sieve aperture, because standard sieve apertures are in constant ratio. Minus 200-mesh is generally assumed as equivalent to 37 microns in size. By definition, the ordinal number multiplied by the per cent material of any size is equal to the energy units in the material of that size in a unit weight of sample. The sum of all energy units is the energy units content of a unit weight of sample, whether it be crusher feed or product. The difference between the energy units in the product and that in the feed is the tangible result of the work input per unit weight of feed. From this the amount of work necessary for one energy unit may be calculated. This has been done for a quartz crushing-test made at the Intermountain Experiment Station of the U. S. Bureau of Mines at Salt Lake City, in which the net work going to crushing was carefully measured. The results of this crushing test are given in Table 1.'

Jan 1, 1929

By Augustus Locke

MY conclusions apply to the engineer in California ore hunting; and, because the product has been overwhelmingly gold, that means gold-ore hunting. But, I wish to think of ore hunting, not as employment for engineers, but as engineering. I wish, moreover, to think of it as productive of ore in significant quantity. The small mine, even if good, means little. Only new districts, or large extensions of old districts can engage our attention here. The conclusions are summarized as follows: (1) The bright color of California mining history comes from the suddenness and intensity of its outburst of gold. Had the mining been averaged from the start, it would soon have become dimmed among greater industries. For fifty years, California has proceeded as an agricultural, timber and oil, but not a mining region. 1

Jan 1, 1931

By Halbert Powers Gillette

FROM the known laws of physical chemistry I believe it can be shown that progressive mass movement of water solutions in channels has seldom been the means of ore-concentration in veins. It is my purpose in this paper to show that the force known as “osmosis” has been the principal factor in ore-formation. Convection-currents have doubtless supplemented osmosis, and the two working together have been the agencies that have gathered the scattered particles of rare minerals into the larger masses which are called ore. Osmosis is commonly thought of as a vague, feeble force that causes slow diffusion of dissolving matter through the solvent. That it is a measurable force, often of great intensity, few know, except those who are familiar with the laws of modern physical chemistry. Therefore, I may be pardoned for going briefly into the elementary mathematics of osmotic pressure and of convection-currents. The velocity of water moving through any channel is given by the Chézy formula: (1) v = c [/rs], in which r is the hydraulic mean radius; s, the slope of the channel in which gravity is the sole propulsive force; and c, the coefficient of roughness of the sides of the channel. From this formula it is evident that the smaller the channel, the smaller the velocity of water under a constant head. In rock-crevices, therefore, where the head is constant, water moves much more slowly than in large fissures, and in moving through sand or porous rock it is to an even greater degree retarded. Hence, if a mass of water-saturated sand be heated, the finer the sand-grains, the more slowly will the temperature rise at parts remote from the source of heat. Conversely, cooling is retarded the smaller the interstices or channels through which the convection-currents move. The importance of this

Jan 1, 1913

By R. P. Marshall, L. P. Costas

The solid solubility of lithium in aluminum was determined by two independent techniques, electrical resistivity and microhardness, and the results are in close agreement. The solubility limits X-ray diffraction studies of the intermetallic compound LiAl indicate that its composition is nearly independent of temperature when in equilibrium with the terminal solid solution of aluminum. THE investigation of the aluminum-rich portion of the aluminum-lithium system at the Savannah River Laboratory was prompted by the observation that over-aged alloys consistently differed from the equilibrium states predicted by the latest published diagrams. Chemical analyses of these alloys showed their impurity contents to be quite low; therefore, the results obtained should have very nearly coincided with true equilibrium. A survey of the literature disclosed that previous studies had been made with metallographicig or electrical resistivity methods,4'5 but that agreement between results and technique was poor as evidenced in Fig. 1, which also includes the present results for comparison. The discrepancies have been attributed to impurities,3 and this is undoubtedly true in the early work.1'4'5 The latest Studies,''~ conducted with starting materials of higher purity, employed metallographic analysis, a technique that is quite sensitive to local homogeneity and depends strongly on subjective interpretation. In the present work the problem of defining solubility limits was approached in two ways. The first measured a physical property, electrical resistivity, at the equilibrium temperature. The second, a micro-hardness characterization of a diffusion zone, is a room temperature evaluation of a mechanical property under conditions removed from equilibrium. A close correlation between two such basically different approaches would strongly justify confidence in the results. I) MEASUREMENT OF SOLUBILITY OF LITHIUM IN ALUMINUM BY ELECTRICAL RESISTIVITY Experimental Procedure. Alloys for electrical resistivity measurements were made by melting and

Jan 1, 1962

Alexander Forsyth, Southport, Me. (communication to the Secretary): In Mr. Irving's able and interesting paper he describes minutely the appearance of the wolframite and its association with the refractory siliceous gold-ore. He also describes this gold-ore, but fails to mention the important pockets of metallic gold found in the Lead City occurrence of it. I use the term " metallic " in preference to the more usual " free," for it has been found that this gold is not easily amalgamated. Metallic gold is comparatively rare in the refractory siliceous gold-ores of the Black Hills; hence its occurrence in considerable amounts in the Lead City wolframite district deserves notice. I possess a beautiful specimen from the Harrison mine. It is a lump of drusy, granular ore, about 6 in. in diameter. The gold .is " shot" through it in large and small pin-heads; and in two specially oxidized areas, each about 11/2 in. in diameter, it is peppered full. The famous " Grantz strike," made in the Lead City wolframite locality, produced many beautiful gold specimens. This district affords an excellent example of the repeated discovery of new mineral values upon old ground. By reason of its proximity to the Homestake vein, this wolframite deposit was inevitably traversed many times by experienced geologists, mineralogists and mining engineers, who evidently must have thrown aside, with no thought of wolframite, the lumps of " black iron " lying about. I have the admission of an able geologist that, six months before the wolframite was discovered, he visited some of the very mines where it occurred, and passed it by as magnetic iron-ore. At the time of the discovery, the mineral was scattered over the gold-mine dumps in no small quantities, having been culled as worthless out of the gold-ore. It remained for

Jan 1, 1902

By Charles A. Ashburner

VERY little is known of the economical value of the coal-betas of. the State of Texas. The first authentic statement in regard to their occurrence is that contained in the reports of the United States Explorations for the Pacific Railroad, near the 32d parallel of latitude, published in 1853-55. Professor William P. Blake reports, "that a number of seams of bituminous coal, varying, in thickness from two to four feet, have been opened along the Brazos River, in Young County, about one hundred and fifty miles west of Fort North." Dr: Shumard also states, "that the characteristic fossil forms of the Carboniferous Era have been found with this coal, and considers the ago of the formation established. Fossils obtained from the carboniferous limestone remove all doubt of the age of these deposits."† In the spring of 1879, I was called upon by. some Eastern capitalists to make an examination of the Brazos coal-field, in order to obtain the thickness, extent, and value of the coal which could be mined and be- made merchantable for steam, heating, and metallurgical purposes. The demand for coal in this section of the country is great, and a fuel. which in our Eastern markets might be considered of inferior quality, would here find a ready sale. It must be remembered that the market value of a coal does not depend upon its absolute purity, but upon its actual value in heat units which it is capable of producing. A poor coal which can be cheaply mined near the: consumer, is infinitely more remunerative to a mining company than a superior coal whose cost to the consumer is greatly increased by high mining charges and railroad freights. The value of the Texan coals does not depend upon their purity but upon their low first cost and nearness to a market. A glance at a geological map of the United States, will show that the Brazos coal-field is the extreme southwestern extension of what may be called the Missourian, Fourth or Western, bituminous coal * I am permitted by the gentlemen for whom the examination was made to publish the general statements contained in this paper. † Macfarlane's Coal Regions of America. More recently brief mention has been made of the coal-field in the pamphlets of the State geological survey. These reports are, however, too general, too indefinite, and too impracticable to permit of any conclusions as to the value of the coal as an economical, merchantable fuel.

Jan 1, 1881

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

By L. G. Austin

My first contact with industrial milling was during the time I worked in the electricity generating industry in the United Kingdom. In visits to power stations to investigate either deposits in the boiler furnaces or polluting deposits settling around the stacks. I had to check the performance of the vertical coal pulverizers, since poor pulverization aggravated both problems. Naturally, then, when I came to the USA in 1957 to take a PhD in fuel technology at Penn State, I was put to work to review the science of coal pulverization. After this reviewing, I was completely confused. On one hand, there was a well-developed understanding of stress-strain equations, and a rapidly developing knowledge of how stressed, brittle solids fractured, based on the Grifith crack theory. On the other hand, reading in the grinding literature gave me: -Kick's Law, which was clearly not correct in the light of modem fracture theory; -Rittinger's Law, which was also clearly not correct; -Bond's Third Law of Comminution, which was claimed to have something to do with the Grifith crack theory, but where the connection between the two was made by intuitive pseudo-scientific reasoning I could not accept; -the choice of mill motor power for the most common type of coal mill, the Raymond pulverizer, was calculated from the fan power required to move air through the mill. Although I could accept the empirical connection between the two, it made no sense from the point of view of fracture energy. Even today, most books or review chapters on size reduction start from these laws. Incorrect statements abound in the literature, such as "the Hardgrove Index is based on Rittinger's Law," which it is not, "The Bond theory states that work input is proportional to new crack tip length produced in particle breakage," which is not true, etc. My own test work showed that these "laws" did not fit the data for grinding of coal. At about this time, Epstein (1948) and Broadbent and Callcott (1956), following the original work by R.L. Brown (1941) at the British Coal Utilization Research Association, proposed describing breakage as a series of fracture stages. I took their concepts and developed the basic differential equation for a batch grinding process continuous in time, analogous to a batch chemical reactor. Robin Gardner then joined the project and did his PhD on treating batch grinding in the same way as a batch chemical reactor. He found that the basic equation had already been partially derived by Sedlatschek and Bass (1953) in Ger- many. We confirmed experimentally the validity of the equations for describing batch grinding (1962) and formulated the equation describing steady-state continuous grinding in a fully-mixed mill. At about the time this work was published, Gaudin and Meloy (1962) and Filippov (1961) independently published essentially the same equations, but without experimental proof of the validity of the concepts. I will give a brief overview of what these beginnings had led to in the design of mills for size and power, and show some of the results of this more detailed understanding of grinding processes. Concepts of Fracture Mills such as tumbling ball, rod, pebble and autogenous mills and vertical mills such as the Raymond, and E-type, apply compressive stress to lumps or particles relatively slowly. Compressive stress applied to a particle of an elastic brittle solid imparts overall strain energy to the solid and produces local regions of tensile stress, [(Fig. 1)] (Berenbaum and Brodie, 1959).

Jan 1, 1985

By Ihor A. Kunasz

Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. However, with the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, presently exploited by Foote Mineral Co., and the Great Salt Lake of Utah, to be exploited by the Great Salt Lake Chemicals Corp., have been defined as major sources of lithium. Also a lithium-bearing brine has been discovered in Chile. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close down their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938. Its ionic radius is 0.60A and its charge is + 1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO)/Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns. 1955). Genetically, the pegmatites are associated kith neigh- boring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their respective distance from the granitic bodies to which they are genetically related (Mulligan, 1965). Lithium is also found in small proportions in a variety of rocks. The average lithium

Jan 1, 1975

By R. H. Lee

WITHOUT doubt, one of the most frequent and serious annoyances connected with the practical running of a blast-furnace, especially in single-furnace plants, is caused by low steam, in spite of the fact that all boilers at blast-furnaces have grates for burning coal, and that coal is more or less continuously burned upon them, from three to a dozen men being pretty constantly engaged around the boilers as firemen or coal- and ash-handlers. At times, when the furnace is ? tight," all available men are put on to assist the regular firemen; yet sufficient steam cannot be got to keep the engines up to their regular number of revolutions, while the stoves, deprived of the gas which has been sent to the boilers, run cold, so that, when the furnace loosens-up and resumes the regular rate of driving, the blast is very considerably below normal temperature, and a.' cold," or at best a " high-sulphur," east is the result. Again, it often happens that a furnace, running at its best, becomes temporarily a little too hot; the pressure rises; the amount of gas made' is diminished; the steam soon commences to go down; and a small scaffold is likely to form before the furnace has been brought back to the proper rate of driving, and thus enabled to take its regular amount of blast. The usual remedy is either to "jerk" the furnace by a sudden, brief intermission in blowing, or to cool the furnace by lowering the heat of the blast; but if the lower blast-temperature be maintained too long, the hearth and descending stock may be cooled below the " critical temperature " mentioned by Mr. .Johnson, and the furnace may go to the other extreme, and become cold. This is especially the case when coal or coke, high in sulphur, is used:

Jul 1, 1906

By Henry A. Mather

While this device is not new in its inception, its peculiar advantages failed to be of practical utility until furnace-builders instituted the mechanical reform of supporting the upper and lower water-jackets by hanging them from an I-beam frame, independently upheld by iron columns, instead of resting the entire weight of structure on the bottom, as practice formerly prescribed. The Colorado Iron Works were among the first to build copper-furnaces of this description, and the device, illustrated herewith, has been installed by them in three recent plants,—two furnaces for the Westinghouse interests near Ely, Vermont, and one for the Grand Prize Copper Company, of Gila county, Arizona. The jack-screw supports (Figs. 1 and 2) and the familiar iron bottom of former practice are retained as integral parts of this new furnace-bottom. And, instead of resting inert on the tapfloor of the furnace-room, the jack-screws are supported on and bolted to two I-beams the length of the furnace, placed immediately beneath, and parallel to, its sides. These I-beams are bolted to, and supported by, three steel axles equipped with small flanged wheels, the whole constituting a carriage, which runs freely on a track. The entire apparatus is movable or rigid at will, for the wheels are easily braced, if the tension of the tightened jack-screws does not serve to hold the whole in position. The advantages of this design will be at once apparent to those who have had practical experience in barring furnaces provided with stationary iron bottoms. It is a well-known fact that the larger part of the time occupied in cleaning and preparing a frozen furnace for active service is necessitated by working in a confined place where the temperature is uncomfortable, and that in such case the débris must be removed from

Jan 1, 1903

By W. H. Geis

The following pages summarize the causes that led to the suggestion of unit operation of the paloma field, the organization of com-mittees, preparation of the Paloma Operators Agreement and the reasons for rejection of the plan. Introduction Long ago an Austrian physicist observed that under certain conditions the condensation of a liquid from gaseous mixtures resulted from pressure reduction. Some 50 years later he would have known that his research was not in vain. He would have seen a group of serious operators and engineers seeking to apply that principle to a conservation . program for unitized production in the Paloma gas field—but he would also have been saddened to see that forces unsympathetic to the application of science in oil production, with little or no appreciation of modern methods and the advantages of cooperation, so far have prevented the adoption of that program. Soon after the Paloma field was discovered it was realized that all the hydrocarbons in the reservoir existed in the gaseous phase. This condition was confirmed over a large area. Therefore, if the field was to be properly exploited with the greatest ultimate recovery of condensate, the hydrocarbons in the reservoir must be produced in the single or gas phase. They must be cautiously extracted with the least possible reduction of the natural pressure. If this could be accomplished, or if artificial pressure control were utilized, the condensation and underground loss of the valuable distillate would be preventable—otherwise it would not be. Wholehearted cooperation of all oper-ators was required in order to accomplish the conservation purposes of the program. To this end the production engineers of the several companies concerned lent their time and talents. They fully investigated the physical relationships of the products within the complicated gaseous mixture, prepared extensive reports on the subject and drew up a reasonably efficient plan of operations, which now is commonly called the "Paloma Unit Plan" but actually was entitled "The Paloma Operators Agreement." All of the engineers were not in perfect agreement on all the features of the plan, or even on all the engineering principles. However, it is safe to say that on all the important or essential factors there was a unanimity of opinion, particularly as to the objectives. These were fairly simple and reduce to one controlling item, "pressure control" by cycling or recycling. Organization The principal operators initiated the program by calling a meeting of all the lessees in the area, at which an organization was perfected, known as the "Paloma Operators Committee." Various subcommittees were appointed to expedite the work, including an "Engineering Committee." These func-tioned in a businesslike manner, frequently reported to the superior committee and

Jan 1, 1942