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By Sherwin F. Kelly

SINCE we used Chief Buehler's name last year to give our annual report a semblance of respectability, we can follow the good precedent thus established by telling of the work his Missouri State organization has been carrying on, as reported by H. S. McQueen. Considerable value is set upon their magrletorneter working which has covered over 13,000 sq. mi.), for the indications it gives of the major structural features of the region. Numerous geological problems have been tackled Ly resistivity techniques, among which are the locating and outlining of filled sink deposits of sulphides, of iron ore, and of fire clay; tracing of faults and solution channels; mapping of the preglacial structural pattern; measurement of depth of overburden; and

Jan 1, 1937

By D. J. McAdam

As shown in three recent papers by the author, in two papers by McAdam and Mebs, and in a paper by McAdam, Mebs, and Geil," the technical cohesive strength of a metal, in any particular state as regards mechanical treatment and heat-treatment, cannot be represented by a single stress value, but must be represented by a diagram with the principal stressest as coordinates. Each point on the boundary of such a diagram represents a technical cohesion limit. The technical cohesive strength thus comprises an infinite number of technical cohesion limits, each representing fracture under a specific stress combination. Moreover, neither the yield strength1 nor the ultimate strength can be represented completely by a single stress value, but must be represented by a diagram with the principal stresses as coordinates. All combinations of the principal stresses may be classified in three groups as illustrated by Fig. I. Fig. Ia shows three typical stress combinations with no two principal stresses equal. The magnitude of each principal stress is indicated qualitatively by the length of the arrow. Arrows pointing away from the cube indicate tensile stresses; arrows pointing toward the cube indicate compressive stresses. Typical stress combinations with two principal stresses equal are illustrated in Figs. rb and Ic. Such stress combinations would be produced by subjecting a cylinder to combinations of uniform axial and radial stresses. The uniform radial stress may be resolved into two equal principal stresses. with the mutually perpendicular directions rotatable around the axis of the cylinder. Fig. ib shows stress combinations with Sz equal to The greatest principal stress is in the axial direction, and the stress combination tends to cause either absolute or relative increase in length.* Fig. u shows stress combinations with S2 equal to St. The greatest principal stress is in the radial direction, and the combination tends to cause either absolute or relative decrease in length. The complete representation of either technical cohesive strength, yield strength, or ultimate strength generally requires a three-dimensional diagram. When two of the principal stresses are kept equal, however, the strength of a metal may be represented by a two-dimensional diagram with the coordinates representing the axial and radial stresses.6-II In this paper, attention will be confined almost entirely to stress combinations with two of the prin-

Jan 1, 1945

By Clarence E. Sims

An effort has been made to give both a comprehensive and simplified picture of the origin, modes of formation, and characteristics of nonmetallic inclusions in steel. Exogenous inclusions, those formed by mechanical entrainment or heterogeneous reaction, have their principal source in ladle refractories. Mechanical emulsion is not considered a likely mechanism. Endogenous inclusions, resulting from homogeneous reactions, are formed mainly during cooling and freezing. They are principally oxides and sulfides but include some nitrides and carbides. Deoxidation affects both the quantity and character of such oxide inclusions and significantly affects the size and shape of sulfides. The importance of inclusions is largely in their effect on mechanical properties. It is fitting and proper that we should honor the memory of those technical giants who have left such a rich heritage to our profession. Today, according to annual custom, we pay tribute to such a man. To have been chosen to play a part in this observance prompts in me an inordinate pride while I am humble before the responsibilities of my task. The ranks are growing thin of those who had the good fortune to come under the personal influence of Professor Howe, but the number who continue to benefit from his legacy of technical wisdom con-stantly increases. I am among the latter. One has only to read his works to appreciate his unusual ability to take data and observations from many sources and give them a clear and comprehensive

Jan 1, 1960

By Arthur Forsyth

A SEARCH through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1.

Jan 1, 1940

By L. C. Graton

The federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal industries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Because of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final and may conceivably be very materially increased. For 1918, the taxes are expected to be still greater, but no compilations are yet available. Taxes at a high rate are to continue indefinitely. The subject is clearly of gravest import to the mining industry in particular. The Commissioner of Internal Revenue, who is charged by law with the administration and collection of the taxes, is determined that these functions shall be performed in a just and businesslike way. Fairness and finality are to be the chief objectives. In view of the peculiar conditions that attach to the tax program as applied to mines and other wasting industries, like oil, gas, and timber, the Commissioner has resorted to professional advice and assistance by manning a Sub-division of Natural Resources with competent engineers, brought in from the several industries, into whose hands he has placed for solution the technical questions involved. These engineers have a two-fold duty: (1) to devote to the solution of these problems their own knowledge and experience; (2) through their acquaintance with their respective industries, and with the men engaged in those industries, to focus upon these problems, by conferences and otherwise, the best opinion of the country. The principal object of this paper is to acquaint the mining profession with the attitude of the

Jan 1, 1923

By L. C. Graton

The federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal industries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Because of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final and may conceivably be very materially increased. For 1918, the taxes are expected to be still greater, but no compilations are yet available. Taxes at a high rate are to continue indefinitely. The subject is clearly of gravest import to the mining industry in particular. The Commissioner of Internal Revenue, who is charged by law with the administration and collection of the taxes, is determined that these functions shall be performed in a just and businesslike way. Fairness and finality are to be the chief objectives. In view of the peculiar conditions that attach to the tax program as applied to mines and other wasting industries, like oil, gas, and timber, the Commissioner has resorted to professional advice and assistance by manning a Sub-division of Natural Resources with competent engineers, brought in from the several industries, into whose hands he has placed for solution the technical questions involved. These engineers have a two-fold duty: (1) to devote to the solution of these problems their own knowledge and experience; (2) through their acquaintance with their respective industries, and with the men engaged in those industries, to focus upon these problems, by conferences and otherwise, the best opinion of the country. The principal object of this paper is to acquaint the mining profession with the attitude of the

Jan 1, 1923

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By Prince Lazarovich, Hrebelianovich

I WAS asked by the chairman of one of the Sessions on Employment Problems to talk about the viewpoint of the foreign workingman. I am not a workingman. I have never done what a work-hand might call an honest day's labor; that is, I have never been in a factory or manufacturing plant or in a mine, though in truth, hard work and I are well acquainted. I was a soldier, am an engineer, have long been actively interested in the most important waterway construction in the near East, have served politics and diplomacy, written books and lectured at universities. My knowledge of the foreign workingman in this country comes from the fact that my own compatriots here at various times came to me and appealed for advice and help, and last year I was asked by the employment manager of a corporation to undertake a welfare job at one of their plants. I went out, saw the plant, talked with the superintendent and outlined certain of my ideas which he personally heartily approved, but which did not find favor with those higher up. I approach the subject of the foreign workman's point of view with the understanding that the industrial employer's effort is for the maximum of efficiency. I am conversant with labor conditions abroad both in industry and agriculture. What I have learned of industrial conditions in America as they affect the foreign immigrant has been chiefly gathered from the cases referred to of foreign workmen who from time to time have come to me with their troubles. In the course of those investigations, in order to give whatever help or advice was possible, I have been impressed with the fact that the great United States industries evidently had- pot yet sufficiently recognized the value of studying the conditions of the workingman in the lands of his origin across the seas. A careful study of that which could be called the moral element in connection with its foreign labor would give industry a knowledge of the man's reason for coming, what' grievances he brings with him, his hopes for a future, and the peculiar character of his capacities. The employer would thereby be enabled to meet the man, to be helpful to him, to aid him and at the same time promote industrial efficiency, inasmuch as a workman who believes that he is being dealt with humanly and squarely is contented and satisfied and will give willingly, and even with pride, the best that is in him; justice and a fair deal is all the man wants.

Jan 4, 1918

By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By Robert F. Mehl

THIS essay is an attempt to present the elementary facts and ideas concerning the growth of crystals, especially of metals. Freezing, like all heterogeneous processes, is a process of nucleation and growth; it manifests itself in metallurgy primarily in the freezing of ingots. The preceding paper in this volume discusses nucleation; the paper to follow describes ingot solidification. The present paper will treat of the growth of nuclei to large crystals, embracing a long series of phenomena, many of which are familiar to metallurgists.† Crystal growth, it will be immediately noted, occurs not only in the freezing of metals, but in the freezing of all substances; and it is a prominent and familiar phenomenon in crystallization from solutions, aqueous or otherwise, and in crystallization from the vapor phase. It will be necessary to include such systems in this discussion, for so much of value to metallurgists has been learned from their study. Apart from this, so far as metals are concerned, it will be simpler to limit the discussion to the freezing of pure metals and of solid solutions. Other types of freezing-eutectic, peritectic, etc.-will be excluded, though they have much of interest and of importance. BASIC MECHANISM OF FREEZING Ideally, nucleation and growth processes can best be considered from the point of view of isothermal reaction and upon the assumption of random nucleation. In. such an ideal case, nuclei form at random, and at a characteristic rate either constant or changing with time, and grow to spherulites at a characteristic rate, constant or changing with time, Fig. I.. On the simplest assumption, the reaction rate-in this case the rate of freezing-is a resultant of these two component rates. The reaction rate equation may be written in terms of these two component rates. The formation of pearlite from austenite closely approaches this ideal case. The ideal case forms a very useful point of departure in considering real cases. Various factors of reality produce deviations from this assumed ideality. In freezing, the isotropic medium, the melt, passes to the anisotropic solid, the crystal. Crystals are lattices of atoms, and the unit cell is often referred to as a crystal unit. Rosenhain, many years ago, represented the nucleation and growth process on freezing in the manner shown in Fig. 2, feeling, intuitively, that there must be some crystal unit in crystal growth. It now appears that this may be true, though his picture requires much elaboration. The greatest deviation from ideality lies in the nonisothermal nature of the freezing process in metals. To approach this properly it should be recalled that many nonmetallic substances freeze slowly. Tammann, to whom we owe the classic approach, studied complex organic materials in which (as in the case of eutectoid steels at high

Jan 1, 1951

Jan 1, 1913

By Stanley Reichert

The manganese deposits of the Embree Iron Co., Embreeville, Tenn., are thought to be fairly typical and representative of the East Tennessee type of deposit, and so to warrent rather detailed description. The methods used by the Embree Iron Co. for prospecting and mining, and to a lesser extent for milling; should therefore be applicable to other East Tennessee manganese deposits, as yet' undeveloped. Early History and Discovery of Manganese Brown iron ore (limonite) was mined by the Embree Iron Co. at various times from 1890 to 1910. The early method was simply pick-and-shovel mining in open pits. Later hydraulic giants were used and sluice lines carried the ore down the mountain slopes to log washers.. During this phase of mining, manganese ore was discovered under the iron ore in some of the pits. In other areas oxidized zinc ore was found under the iron. It thus happened that the valuable zinc deposits were discovered in 1914. During the World War period, from 1914 to 1918, there was sporadic prospecting for manganese ore among the abandoned iron workings, but the main activity then centered around the recently discovered lead and zinc deposits. It was not until 1934 that manganese mining began in earnest, under the supervision of R. D. Pritchett, Mine Superintendent. Geology of the Manganese Deposits United States Geological Survey Folios 151 (Roan Mountain) and 118 (Greeneville show that Bumpass Cove is a synclinal structure thrust faulted along the southeast flank, but with normal sequence of strata along the northwest flank. Fig, l. shows the areal geology of Bumpass Cove as taken from the folios superposed on the U.S.G.S. -T.V.A. 1/24,000 topographic maps of the Erwin and Telford 7 ½ minute sheets. The manganese mines occur near the contact of the unfaulted Shady dolomite and the Erwin quartzite. This contact zone is deeply weathered, with overburden averaging 40 to 60 ft. thick. The material overlying' the bedrock along this normal contact is a very tough, plastic clay, termed "buckfat" or "ocher" by the miners. It is not a true ocher, however, in the sense of having commercial value. The manganese deposits occur along this "ocher" band. Fig. 1 also shows how the manganese deposits occur along the broad topographic terrace between the 2100 and 2200-ft. contour lines. This terrace lies at the foot the Erwin quartz ridge. Apparently it is the topographic is expression of the deeply weathered zone along the Shady-Erwin contact.

Jan 1, 1941

By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By Herbert Clark Hoover, Lou Henry Hoover

QUESTIONS of assaying were explained in the last Book, and I have now come to a greater task, that is, to the description of how we extract the metals. First of all I will explain the method of preparing the ore1 ; for since Nature usually creates metals in an impure state, mixed with earth, stones, and solidified juices, it is necessary to separate most of these impurities from the ores as far as can be, before they are smelted, and therefore I will now describe the methods by which the ores are sorted, broken with hammers, burnt, crushed with stamps, ground into powder, sifted, washed, roasted, and calcineda.

Jan 1, 1950

Jan 1, 1968

By John E. Hagni, Richard D. Hagni

ORE.ID, a microcomputer program, rapidly searches a database of the principal properties for 573 ore minerals. Searches may be performed on any or all of the following properties: mean Vickers hardness, Talmage hardness, mean reflectance, strength of anisotropism, and colors and tints of the mineral and its internal reflections. Data from the International Mineralogical Association - Commission on Ore Microscopy data card file have been used when available. The program displays the number and type of data matches for each mineral found, displays their chemical components, and allows the range to be narrowed or widened for each of the identification properties for repeated searches, if desired. ORE.ID is much more rapid, allows for the use of more identification properties, and involves more ore minerals than any previous identification system.

Jan 1, 1985

By J. Chipman, J. C. Fulton

Reduction of silicon from blast-furnace-type slags by carbon-saturated iron is a very slow reaction even under conditions of rapid stirring. Equilibrium under atmospheric pressure of carbon monoxide was approached from both sides, and the silica-silicon relation was established at temperatures of 1425º to 1700°C for slags containing up to 20 pct Al2O3. Silicon carbide is formed by reaction of graphite with high silica slags and the conditions for its formation were determined. Activities of SiO2 and of CaO in their binary solutions at 1600°C were determined. The effects on the activity of SiO2 were established for additions of 10 to 20 pct AI2O3 and of 10 pct MgO. STUDIES of chemical reactions between blast-*>-5 furnace slags and metal have been focussed on the transfer of sulphur from metal to slag. The important role which silica reduction plays in this process' has led to a study of the transfer of silicon from slag to metal and the equilibrium represented by the equation SiO2 (in slag) + 2C (graphite) = Si + 2CO (g). [I.] The authors2 have published an account of the experimental method employed in attacking this problem and of three series of experimental results at 1600°C. This paper contains data on some additional compositions and extends the observations to cover the temperature range 1425° to 1700°C. The data are used to determine the activity of silica in the slags. As in the earlier experiments, the atmosphere was carbon monoxide which flowed through the furnace at 150 ml per min. In certain heats designated in the tables and figures, the gas was bubbled through the melt using a graphite tube. The latter increased in porosity during a run and in some cases bubbling ceased as indicated by cessation of surging. Some results were discarded for this reason. Experimental Results The new data are shown in Tables I through V and both old and new data are plotted in Figs. 1

Jan 1, 1955