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By Laurence Delisle

The aim of this paper is the description of a technique to be applied to the study of sections of metal powder particles, less than 20 microns in diam. with the electron microscope, by the replica method, using for replica a material such as formvar or parlodion. This work originated with the study of particles of tungsten powders. Such particles were too small to be examined in sufficient detail with the light microscope. On the other hand, examination with the electron microscope of the powders dispersed in the supporting film was not found satisfactory because: 1. It did not permit differentiating between single particles and aggregates. 2. It did not show the true outlines of the particles but only the projection of a whole surface. 3. No details appeared. For that reason it was attempted to make replicas of sections of the particles imbedded in a mounting material suitable for polishing and etching. The method proved satisfactory for the examination of tungsten powder and was then extended to car-bonyl nickel and carbonyl iron powders. Procedure Several mounting materials commonly used in ordinary metallography were investigated. The problem consisted in finding a mounting material

Jan 1, 1950

By Arthur E. Granger

IN the early days of the science, and until the recent past, geologists worked as individuals or in small groups. Prior to 1930 perhaps the largest single group under one administrative head was the Geologic Branch (now Division) of the U. S. Geological Survey, which employed at that time (including temporary help) 100 to 150 geologists. Today that same unit employs some 1500. In industry some companies employ as many as 100 geologists in a single department. These numbers obviously pose a need for administration. The basic qualifications for good administration are the same for any group of human beings, but the administration of geologists presents some special problems. Choosing Administrative Personnel: There are two kinds of personnel needs: 1) technical, which requires professional geologists who have proved their capabilities in the field, and 2) clerical and fiscal, which provide the necessary supporting or housekeeping functions. This discussion will be concerned only with the first category, except to point out the need for competent and understanding help from clerical and fiscal people and close relationship between top administration, technical or professional personnel, and the clerical and fiscal groups.

Jan 7, 1957

By A. G. Willard

Quantification of size, shape and composition has been one of the more difficult areas for those concerned with fine particle processing of coal.' Image analysers fed by optical microscopes and by scanning electron microscopes possessing backscatter detectors and energy dispersive facilities now offer techniques to improve the speed and precision of previous methods. This paper discusses the methodology and procedural difficulties associated with the microanalysis of coal. Photographs show display quality on the image analyser monitor and the equipment mentioned. Data illustrating several of the procedures are included. The major portion of data for design and operation of plant for fine particle processing depends on information regarding size, shape and composition of granular material. The lower limits of particle sizes become more important as lower grade deposits are mined. Because of the trends towards treatment of finer materials, the use of image analysis offers advantages in time, effort and accuracy. As energy becomes more critical, the above applies especially to coal processing. The Zeiss Microvideomat 2, a leading member of the second generation instruments, is now available for image analysis. There is a precision television scanning system with monochrome camera, display, control panel and central processor (see Figure 1).

Jan 1, 1980

By Shiou-Chuan Sun

THE effects of oxidation on the flotation behavior of sulphide minerals have been extensively studied,1-3 but no similar study has been made of coals. Coals of bituminous and lower rank undergo atmospheric oxidation during mining and storage, and their degree of oxidizing increases with temperature4,5 and time of exposure.6 The problem of recovering fine oxidized coal from culm piles, rivers, and streams by froth flotation has become increasingly important to the coal industry as well as to those concerned with air and stream pollution. This paper describes the flotation behavior of oxidized and unoxidized coals and carbons in the presence of oily collectors and presents the reagents found effective in the flotation of oxidized coals and carbons. Except where otherwise stated, flotation tests were performed in a 50-g Denver flotation cell. Solid feed for each test was 30 g, and the pulp dilution was kept at 8.5. The -65 mesh coal sample was wetted by agitation with water in the flotation cell for 6 min, then conditioned with a predetermined amount of collector for 2 min, and finally floated with pine oil as frother for 3 min.

Jan 4, 1954

ONE of the perplexing problems that face the translator of an old technical treatise is the question of terms for units of weight and measure. We have used an English word only when it is linguistically equivalent to the Italian one and is a unit of approximately the same size. Libbra and oncia thus become pound and ounce, for the actual weights were within 10 per cent of the modem Troy weights. On, the other hand, the length measures braccio, palmo, and dito, which could be rendered literally as arm, palm, and finger or digit, respectively, have no good English metrological equivalents and it has seemed best to retain the Italian words. The exact transfer of Biringuccio's weights and measures into modern terms is impossible because of the uncertainty as to his standards. Even as late as 1803, when the metric system was first introduced into Italy, practically every city had its own standards. There were, for example, at least eight different palmi, varying from 22.3 to 29.2 centimeters. The values listed below for the various units mentioned by Biringuccio are the Florentine ones, which were also used in Siena and Tuscany: [ ]

Jan 1, 1942

By Thomas Cox

This paper makes no claim to any new idea; it simply reviews the Treasury Department Regulations pertaining to the practical application of depreciation and depletion and other allowances governing taxation of oil and gas properties. Other methods may be existent, but as they may not conform to the legal status they must be discarded. In complying with the present laws governing the industry with regard to taxation and the allowable deductions therefrom, the following considerations are essential: Depletion, depreciation, amortization, other allowances, and items not, deductible. It is definitely understood that depletion is the loss or exhaustion sustained in the continuous operating of an oil and gas property, and that each unit of oil or gas taken out reduces the value of the property until its final exhaustion. Depletion applies only to the natural deposits of oil and gas due to their removal in the course of exploitation of any property. Depreciation is defined to cover the waste of assets due to exhaustion, wear and tear, and obsolescence of the physical property, and is separate and distinct from depletion; its allowance is that amount which should be set aside for the taxable year in such sums as for the useful life of the property will suffice to repay its original cost—or its value as of Mar. 1, 1913, if acquired by the taxpayer before that date—less the salvage value at the end of such useful life. Amortization is allowed for such facilities as were built or acquired on or after Apr. 6, 1917, for the production of articles contributing to the prosecution of the war and, in the case of vessels, those built and acquired after that date. The amount to be extinguished, in general, is the excess of the unextinguished or unrecovered cost of the property over its maximum value under stable post-war conditions. Claims for amortization must be unmistakably differentiated in the returns from all other claims of depreciation. The taxpayer is also required to furnish full information with the claims for amortization to the full satisfaction of the Commissioner. Further reference is directed to the specific rules and regulations for making these claims.

Jan 1, 1921

By Carl E. Swartz

ALTHOUGH a number of articles appeared during the war advocating the use of cadmium in lead-tin solders, very little information of value can be found in the literature regarding the properties of solders containing cadmium. In most of the published articles the cadmium seems to have been considered merely as a partial substitute for tin in a tin-lead alloy rather than as an essential constituent of a ternary alloy. The primary object of the substitution of cadmium for tin was to lessen the amount of tin required, at a time when the latter was scarce and high-priced, and thus to produce a cheaper solder. While this object was accomplished, the new properties resulting from a change from a binary lead-tin alloy to a ternary lead-tin-cadmium alloy were not given proper consideration in many cases. For the past few years, the American Smelting & Refining Co. has been marketing a very considerable amount of cadmium in the form of lead-tin-cadmium alloys for use as solders for certain special purposes, and the successful use of these solders suggested that if more extensive knowledge were available concerning the properties of lead-tin-cadmium alloys of various compositions their field of usefulness might be materially extended. The investigation described in the present paper was undertaken to obtain this information and, by means of tests under conditions approaching those of practical use, to determine the suitability of cadmium solders for various purposes. CHARACTERISTICS AND REQUIREMENTS OF SOLDERS IN GENERAL General Physical Properties.-When cast into bars, solder should present a smooth and bright appearance free from oxide inclusions and bubbles. Ductility should be as great as possible without sacrificing tensile strength, and vice versa. Hardness and specific gravity are not of any great importance. Melting Characteristics.-The melting or solidification range is important. This statement applies both to the extent of the range and to the actual temperature at which complete solidification occurs. A rather narrow solidification range is desirable in soft solders in order that solidification may take place quickly. The solder should have high fluidity at temperatures only slightly above its melting range. For a

Jan 1, 1928

In our sessions devoted to geophysical prospecting, the greater part of the time heretofore has been given to the presentation of theoretical subjects or highly technical details by specialists directly engaged in the development and perfection of the various methods. This was necessarily so, for we wanted such information available for the benefit of other workers and for our members who were anxious to gain a reliable understanding of the principles involved, to enable them to form an opinion of the adaptability of this new technique to their special problems. The methods have now been actively applied by many reliable organizations for several years and in this period there has been opportunity for operating mining men, engineers and geologists to appraise them. We therefore felt that it would be desirable at this meeting to give some time to interchange of opinion concerning results from actual cases. Consequently, the Committee on Geophysical Methods of Pros pecting sent out letters of inquiry to numerous mining people, asking for frank statements of opinion based on results from geophysical surveys at their properties. We have received many replies, among which 30 or more are of specific interest. On the whole, the point of view is remarkably uniform. Except for one or two who were, perhaps, a bit irritated, the operating men who have replied consider the methods to be capable of yielding valuable information when suitable conditions exist. Their attitude is definitely one of tolerance and of confidence in the integrity and sincerity of the outstanding workers. There is, however, a very general feeling that the chances of attaining positive and trustworthy results are small unless the work is directed by, or at least carried on with the close cooperation of, a geologist or mining man who is thoroughly familiar with the local geologic and mineralogic conditions and with the relations of the orebodies to rocks and structure. From certain comments, I am inclined to think that some operators are not greatly impressed with the cheapness of the work. Probably they are not attaching much weight to cost per acre, but are thinking primarily of total cost in terms of significant results obtained. It is

Jan 1, 1932

By Y. Okahara, I. Iwasaki

Chlorination behaviors of pure iron and manganese oxides were investigated by combining a thermogravimetric analysis (TGA) technique with batch-boat roasting followed by leaching. Ferrous and manganous oxides could be chlorinated readily, but, in the absence of a reductant, the higher oxides of both iron and manganese were dificult to chlorinate. Thermogravimetric analysis curves were drawn to illustrate the complexities of the reactions, and the possible mechanisms were discussed. Then three manganif-erous materials from the Cuyuna Range of Minnesota were treated by a process involving the selective chlorination of manganese followed by leaching. The results were interpreted in the light of the chlorination mechanisms observed on the pure iron and manganese oxides. One of the unsolved problems challenging Minnesota's mining industry is the development of an economic process to utilize the manganiferous iron ores of the Cuyuna Range. Although these ores constitute one of the major domestic reserves of manganese (estimated at 432 million tons'), their grade is too low for them to be mined solely for manganese. The nearly exclusive dependence of the U.S. steelmaking industry on foreign manganese ores has stimulated research over the years in treating the low-grade Cuyuna ores. As a result, a number of processes have been proposed.'-' Among these processes is chlorination. Chlorination is the high-temperature conversion of metallic oxides to chlorides by either chlorine or hydrogen chloride gas, or by solid chlorides of sodium, calcium, or magnesium. The metallic chlorides are then recovered by either vaporization or leaching. Although chlorination is an old art, it has become popular in recent years for the recovery of such new metals as titanium, zirconium, and niobium; for the removal of impurities like copper, lead, and zinc from pyrite cinder for ironmaking raw materials;' and for the segregation roasting of coppera and nickel' ores. The chlorination processes proposed for manganifer-ous iron ores have been relatively few (hydrogen chloride chloridization-leaching, hydrogen chloride and calcium chloride chloridization-volatilization,' and chlo-rination-selective condensation6), due presumably to the economics and to the corrosion problems involved. However, the successful application of chlorination processes to other ores will undoubtedly contribute to technological advancements in the chlorination of man-

Jan 1, 1971

The Manufacturer's Viewpoint A prominent manufacturer of mining 'machinery not long ago expressed himself as being confident that he was securing the best kind of publicity for his product through the advertising pages of the monthly Bulletin of the American Institute of Mining Engineers. Such an expression coming from such a man is highly gratifying; yet it is justifiable when the high quality of reader and subscriber is taken into consideration. In fact, the majority of those using our advertising pages feel the same. It is to be regretted, of course, that others catering to our field do not realize the means at their disposal for presenting the points of interest of their product to the mining man. The question has been asked, " Do your members read their Bulletin?" They not only read the editorial pages, but they "admit being up-to-date enough to peruse the advertising section to "see what is new." The next question the prospective advertiser asks is, " Will the Bulletin bring inquiries?" The answer to this question holds good for any publication having as subscribers those who have purchasing or recommending power-yes, if the article advertised is not a stock one, that has been before the public for any length of time. To secure inquiries on, say, a standard centrifugal pump or any other standard product, the features of which are well known, is a most difficult proposition. Yet, of course, some inquiries are secured, but mostly from those having use for the catalogue or trade literature for reference purposes. It is safe to say that the traceable returns from advertising in trade publications hardly, if at all, pay for the advertising. The real returns are intangible, and result from the constant publicity, and keeping ?everlastingly at it." Who can say what subconscious effect is taking place when an advertisement is "glanced at," to say nothing of the effect produced when the copy is attractive and interests the reader. Time after time it has been proved that sales have been secured as a result of an advertisement, yet no inquiry had been made directly traceable to advertising.

Jan 8, 1915

By Theodore A. Blake

More than a quarter of a century has passed since the introduction of the machine known as the Blake crusher, the invention of Eli W. Blake, of New Haven, Conn. Although originally designed for breaking stone for road-metal, its importance for crushing ores of the precious metals, and those of iron, copper, and zinc, as well as emery, phosphates, plaster, etc., mas soon recognized, and for many years its use has been world-wide, and its construction so well known that no special description of it is deemed necessary. Following its introduction, many different machines for the same purpose, containing the same essential features of upright convergent jaws, one of which is movable with respect to the other, hut having some slight modification of such movement (generally a rubbing motion) or of the non-essential method of imparting motion to one or both of the jaws, have been offered to the public for sale and use, but have, as a rule, in time disappeared from the market. If we seek for the reason of the success of the Blake crusher, aside from its simplicity of construction, we shall find it in the adherence to the principle of crushing by simple pressure and careful avoidance of attrition. In this lies the economy of power and of wearingsurfaces. To reduce any hard and brittle material to a fine powder by many different methods—by attrition, impact, or percussion—is a comparatively easy matter; but to accomplish this by the employment of either of the above-mentioned principles involves such a consumption of wearing-surface? (generally iron) or of power, that the numerous devices that have hitherto been presented to the public as solutions of the problem of fine crushing have proved utter and complete failures when tested with reference to the power employed and the wear of iron in doing their work.. Aside from the use of crushers with the harder ores, the only two methods of fine crushing in general use, and, in the writer's opinion, worthy of consideration, are by means of stamps and rolls; the former doing their work by percussion, the latter by pressure, provided

Jan 1, 1885

By Howard A. Meyerhoff

AS a source of mineral wealth, the larger islands of the West Indies have never had an enviable reputation. The Spaniards took possession of them in the sixteenth century hopeful that they would yield gold; but it was not long before they knew the rather rigid limitations of Antillean gold production and were seeking-and finding ---richer deposits of the precious metals in Mexico and on the west coast of South America. Although a great deal of wealth changed hands in the West Indian islands in subsequent years, the fact may be laid to the abundance of pirates and privateers and not to the richness of local ore bodies.

Jan 1, 1941

By J. M. Uys, T. B. King

The solubility of water in silicate melts of various compositions was measured. The basicity of the silicate did not appreciably affect the water solu-bulity at low-base content (acid compositions). Near the orthosilicate composition the solubility increased with basicity for silicates in which the cation displayed a weak ion-oxygen attraction and apparently decreased for those in which the cation showed a strong ion-oxygen attraction; metasilicates of the former class dissolved more water than those of the latter. Temperature had little effect on water solubility. The experimental results are interpreted on the basis of two modes of solution, the contribution of one decreasing, and that of the other increas -ing, with increased melt basicity. In the former, solution occurs through interaction with doubly-bonded oxygen atoms and in the latter, through interaction with singly-bonded oxygen atoms, or, in very basic melts, through reaction with free oxygen ions. THE hydrogen content of a steel melt is in a large measure determined by water dissolved in the slag. In some glasses water may be a major cause of "seeds". Water vapor in the furnace atmosphere is the primary source in both instances. A knowledge of the mechanism of water solution in silicate melts should help in assessment of practical methods for its control in steelmaking and glass refining. Walsh et a1.l measured the water content, expressed as hydrogen, of 40 pct lime-20 pct alumina-40 pct silica and 62 pct manganese oxide-38 pct silica melts as a function of the steam partial pressure, in equilibrium with the melt. Tomlinson 2 and, also, Russell3 investigated this relationship for a molten 30 pct soda-70 pct silica glass. In all three investigations, the solubility of water was found to be proportional to the square root of the partial pressure of steam. Moulson and Roberts 4 confirmed this relationship for a silica glass. On the basis of the square root relationship, Tomlinson2 and Russell3 interpreted the solution reaction as "network-breaking", similar to that expected on the addition of metal oxides to silica. Walsh et al.' postulated two possible modes of solution, one the mechanism suggested by Tomlinson and Russell and the other the reaction of the water molecule with an oxygen ion to form hydroxyl ions. These two modes of solution suggest opposite effects of melt basicity on water solubility. However, little appears to be known about the effect of melt basicity on water solubility. Walsh et a1.l found, in the lime-silica system, that the water content increased slightly with increased basicity. As these authors pointed out, this does not appear to be in accord with their further observation that slags containing little or no silica dissolve very little water. Kurkjian and Russell5 measured the effect of basicity on water solubility in alkali silicates in the composition range 15 to 45 mole pct alkali oxide. They found a minimum in the water content at about 25 mole pct alkali. This was interpreted on the basis of two concurrent solution reacZions; one in which solubility was proportional to the activity of doubly-bonded oxygen and, in the other, proportional to the activity of singly-bonded oxygen. The present work was aimed at establishing the effect of basicity on water solubility in silicate melts over as wide a range of compositions as practical. APPARATUS AND EXPERIMENTAL PROCEDURE The silicate melt was equilibrated with a "carrier-gas" of accurately known water content, quenched, and analyzed for water by a vacuum fusion technique. Some pertinent details of the equilibration procedure, analysis technique, preparation, and handling of the silicates are given below. Gas-Silicate Equilibration. The apparatus used to equilibrate the melt with the gas mixture was similar to that used by Walsh et al.' but with some important modifications.6 Purification trains were provided for nitrogen and hydrogen; whenever air or oxygen was used as carrier gas the nitrogen purifiCation train was used with the copper furnace at room temperature. Gas flow rates were measured with capillary flow meters; bleeders filled with a mixture of dibromo and tribromo ethyl benzene (density about 2 g per cc) were used for convenience in controlling flow rates.

Jan 1, 1963

By R. Bakish, C. S. Barnett

IN experiments on tantalum strained in tension, Bechtold did not observe deformation-twinning even at a temperature as low as that of liquid air.' This is an unexpected behavior for a metal of body-centered-cubic structure. Therefore, it is desirable to determine whether the lack of twinning is an inherent characteristic of this particular metal, or whether the reluctance to twin can be overcome under suitable conditions. The following experiments were performed under conditions favorable to twinning and cleavage in their competition with slip, namely, with impact loading on large-grained sheet at low temperatures. The crystallography of cleavage in tantalum sheet was also investigated carefully because of the remarkable ductility of tantalum at low temperatures and because recent tests on oxygen-embrittled tantalum had disclosed unusual cleavage behavior for a metal of this structure: cleavage primarily on (110) planes and only occasionally on {100}.2 The tantalum, supplied by Fansteel, was of 99.9 pet purity, with the chief impurities being iron (0.03 pet) and carbon (0.03 pet). Coarse grains were produced by the strain-anneal method, the anneal being 4 hr at 2000°C in a vacuum of 10-3 mm Hg, followed by furnace cooling. Impact deformation was applied in various ways: a) by hammer blows on an anvil, the specimen and anvil being immersed in liquid nitrogen ( —196°C), b) by driving a precooled center-punch into the sheet, and c) by bending around a crystallographically determined axis with a hammer blow. The impact-deformation produced bands and slip lines on the surface, Fig. 1. The bands have every appearance of being deformation twins, a) They are tilted with respect to the untwinned surface. b) They have the appearance of Neumann bands in iron, thin lens shape, some having serrated edges. c) The orientation in each is different from that of the surrounding matrix and uniform within a given band, see slip lines within them in Fig. 1. d) Upon repolishing and etching, the difference in orientation and the resemblance to Neumann bands is again evident, Fig. 2. (In this micrograph the slight bend in the bands as they cross grain boundaries was noted frequently and results from the high degree of preferred orientation in the sheet.) e) The bands persist after annealing treatments that would have removed them had they been a low-temperature martensitic phase, e.g., after an anneal of 1/2 hr at 900°C. When back-reflection Laue data were plotted for single-surface analysis of several grains, every trace of the bands in each grain could be explained by (112) planes. In addition, two of the bands were located in space by traces on two surfaces, and these also were found to lie on (112) planes within the error of the stereographic plot. Since (1 12) is the anticipated composition plane for deformation twins in body-centered-cubic metals it is felt that the observations listed above are conclusive evidence for the identification of the bands as twins. Similar tests with impact at —77° and at 25°C produced no twinning. It is concluded that the critical shear stress for slip at the rates of straining used was always low enough to prevent the applied stress from reaching the value required for twinning at these temperatures. It was noted that the serrations along the edges of the twin bands exhibited parallel crystal facets. Several similarly oriented notches are visible in Fig. 1, and a remarkable set is shown in Fig. 3. It appears from Fig. 1 and similar areas that notches are frequently associated with the intersection of a slip line with a twin, although not all such intersections are at notches. In some instances a slip line appears to enter the twin, cross it, reflect from the opposite side and recross it, producing a pattern resembling a notch but without producing the notch itself, see Fig. 1. It is suggested that the stress concentration at the end of a slip line is responsible for these details. The strain energy associated with the pile-up of dislocations at a twin boundary may be lessened by untwin-ning or failing to twin a portion of the twin band, or

Jan 1, 1959

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By R. L. Fleischer, W. F. Hosford

Tensile data for coarse grained aluminum Polycrystals suggest that the "grain size" effect is not due to dislocations piled up at grain boundaries but rather is primarily a relative size effect due to surface crystals being weaker and less confined. STUDIES directed at interpreting hardening of poly-crystalline metals normally identify their strain hardening properties with those in some particular type of single crystal.1"4 The recent recognition in face centered-cubic metals of a nearly linear stage with rapid hardening occuring at comparable rates for both polycrystals and single crystals, suggested that the same process or processes determine both cases and hence that there exists some justification for the use of single crystals to understand polycrystals. Further evidence for the above view may be found by an approach initiated by Chalmers:5 By using bicrystals of controlled orientation it is possible to begin to assemble a polycrystal and also to study grain boundary effects in detail. In this way it has been found that a single grain boundary affects easy glide but not the subsequent stage II hardening.6 This result suggests that a sensitive way to observe grain boundary effects in polycrystals would be to vary grain size and measure easy glide. As will be seen, easy glide is only possible for coarse-grained samples, and hence the results will serve to fill in the gap in measurements between single crystals and bicrystals on one hand and fine-grained polycrystals on the other. One problem inherent in comparing single crystals with polycrystals is the uncertainty as to what slip systems are acting in a polycrystal. To compare the two types of samples, rates of shear hardeninn---L. on the acting -planes are needed. and these may be computed only if it is known what particular systems are active. The acting systems were examined for a coarse-grained polycrystal and it will be shown that the systems supplying the preponderance of slip can be determined with little ambiguity. EXPERIMENTAL PROCEDURE Twelve samples of aluminum were prepared by chill casting into a heated graphite mold, followed by annealing at 635° ± 5°C for 24 hr with an 8-hr fur- nace cool, and finally either etching7 or electropol-ishing.' The samples, with a 7 to 10 cm length between grips and 4.4 by 6.6 mm in cross section, were deformed at a strain rate of about 3 10 -3 . per min in a tensile device which has been described elsewhere.5 The composition was reported by Alcoa as 99.992 pct Al, 0.004 pct Zn, 0.002 pct Cu, 0.001 pct Fe, and 0.001 pct Si; nine samples were deformed while immersed in liquid helium and three in air at room temperature. The stress-strain curve for one of the samples (P-1) deformed at 4.2 "K has been reported previ~usl~.~ This sample was selected for determination of active slip systems. Eighteen of the crystals were examined by optical microscopy to determine the angles of slip line traces and by X-ray back reflection to determine orientation. By this means the slip planes were determined and the resolved shear stress factors for possible slip systems could be computed. Finally each sample was sectioned so that after etching, the number of crystals could be counted for each of ten newly exposed surfaces. The average of these ten values will be termed n, the number of crystals per cross section. Values of 11, varied from 1.9 (nearly bamboo structure) to 12.7. Sketches of typical cross sections appear in Fig. 1. RESULTS AND DISCUSSION: SLIP SYSTEMS 1) Determination of Acting Slip Planes—The stress axis orientation and operative slip planes in eighteen crystals of sample P-1, as determined by slip line traces and crystal orientation, are summarized in Fig. 2. For one of the crystals two planes had a common trace. so that the traces alone did not distinguish which plane or planes were slipping. However it was found that the stress resolving factor for the primary system was 0.386, .while that for the most stressed system in the other plane (indicated bv the dotted arrow) is 0.138. It will be assumed tgerefore that only the primary plane acted. Since the orientations were determined after extending the samples 4 pct, the stress axes may be rotated from their original value by as much as 2 deg in some cases. It is interesting to note that in five crystals only one slip plane acted, in eight two acted, and in five three planes were observed—an average of two slip

Jan 1, 1962

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By R. E. Ogilvie, E. T. Peters

The X-ray Kossel-line method has been used preaioz~sly for measuring lattice parameters to accuracies of 1 part in 100,000.5 A second application of this method is described for determining the crystallographic orientation of a randomly positioned single-crysta1 spherical volume that can he as small as 50 µ in diameter, within accuracy limits of ±1/2 deg. The theory, experimental procedure, and interpretation of Kossel-line patterns and an experimenta1 verification of the predicted orientation relationship of the cph k and fee a Cu-Si phases are presented. This orientation relationship can be described as (111)a, (00.1)k; [110]a [11.0]k. In addition, the lattice parameter of the a phase was found to he a. = 3.62154 ± 0.00014Å. The Kossel-line method when used in conjunction with electron microanalysis is shown to he capable of providing a complete chemical and structural analysis of a given crystal. THE most easily accomplished methods for determining the orientation of a single crystal are variations of the Laue X-ray diffraction method. Although certain materials can be oriented to within ± 1 deg accuracy by observation of exterior macroscopic features, such as etch pits, cleavage faces, or growth features, the Laue method is generally preferred for routine laboratory application. Both back-reflection and transmission patterns are coordinated by appropriate reference charts and are plotted in terms of reflection plane poles (normals) on a stereographic projection. Orientation is deduced by relating the pole distribution (which is fixed by the crystallographic symmetry of the specimen) to two specified external reference directions. The Laue method has several limitations. 1) Orientation can rarely be determined to better than ±l deg accuracy. Principal errors involve inaccuracy in specimen-to-film distance, measurement confidence of individual Laue spots, and stereographic plotting. 2) Because of the indeterminacy of the X-ray wave length diffracted to a given spot, it is not possible to determine supplementary crystallographic data, such as interplanar spacings and lattice parameters. 3) The method is generally limited to specimens of cubic symmetry or to specimens of high symmetry and known structure. 4) The relatively large cross-sectional area of the incident X-ray beam generally precludes the measurement of relative grain orientation in a polycrystalline material.* _____ Several of these limitations can be overcome by application of the Kossel-line method, which has been previously employed for precision lattice-parameter determinations.'-= For this method, a point source of divergent monochromatic X-rays is generated within the crystal by means of an incident electron beam. The divergent X-rays which fulfill the Bragg law are diffracted by the specimen and are recorded on a film placed either in transmission or back reflection. Analysis of the film yields a direct measurement of orientation and lattice-spacing values to an accuracy of ±1/2 pct. As analyses can be obtained from spherical specimen volumes as small as 50 µ in diameter, the method provides a means for structural analysis of second-phase or impurity precipitates within a given matrix. The primary limitation of the Kossel-line method is the requirement for an electron microanalyzer or similar apparatus capable of producing a finely focused electron beam. This paper is designed to present the theory, experimental procedure, and geometrical interpretation of Kossel patterns. The experimentally determined orientation relationship between the k and a phases occurring in the Cu-Si system and a precision measurement of the a lattice parameter are presented as a practical application of the method. THEORY OF KOSSEL LINES Divergent X-ray beam photography utilizes an effective point source of characteristic X-rays which, when diffracted from a single crystal, form numerous diffraction and absorption cones that are recorded on film.7 The cones generated from a source lying within the crystal are called Kossel lines.' Although the X-ray scattering from a divergent point source contained within a crystal is described in terms of Laue dynamical theory,9 the directions of the diffracted spectra can be ade-

Jan 1, 1965

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950

By S. Feuerstein, L. Rice

The effect of low pressures on the flow and fracture behavior of molybdenum is described. For poly crystalline samples, room-temperature tensile tests indicate greater ductility under 10 Torr than under intermediate pressures up to and including atmospheric pressure (760 Torr). In addition, tests conducted at 760 Torr under atmospheres of air, dry nitrogen, and purified argon exhibited no apparent difference in mechanical properties. Critical tests involving baking in situ as well as those involving single-crystal deformation further imply that the ductility effect is a pressure-dependent phenomenon related only to the fracture process. This dependency is discussed in terms of adsorption and diffusion contributions. THE effect of very low pressures on material properties has heretofore been presumed to be important only for substances possessing relatively high vapor pressures at ambient temperatures. Research has therefore been concentrated primarily on organic solids and liquids, and in some instances on metals such as zinc and cadmium. Most vacuum-effect studies' on the mechanical behavior of metals have been performed under conditions of either cyclic loading or creep rupture at elevated temperatures, i.e., over extended time periods. These studies were not restricted to high vapor pressure materials but also encompassed such metals as gold, copper, and nickel. Very little concern, however, was placed upon the importance of a vacuum environment on the mechanical behavior of metals subjected to a simple unidirectional deformation at ambient temperatures. A tension test is generally of short duration as compared to a creep test, and at room temperature vacuum effects if any would be expected to be surface-limited. In early 1963, Kramer and podlaseck2 reported a change in the bulk flow behavior of aluminum single crystals during room-temperature tension tests. The deformations were performed under pressure conditions of 760 to 3.4 X 10-8 Torr and indicated for the first time a vacuum surface effect contributing to the bulk tensile behavior of metal specimens. As a consequence, an experimental program was initiated in this Laboratory to study the effects of ultrahigh-vacuum conditions on the mechanical behavior of metals. The results of a preliminary study on poly-crystalline molybdenum3 revealed, unlike Kramer's observations of changes in the stress-strain behavior, only an increased ductility under ultrahigh vacuum. Flow behaviors were nearly identical for all tests re- gardless of pressure. This paper presents comprehensive results obtained in this area of research. 1) EXPERIMENTAL PROCEDURE Three material categories were used in this study: sintered and are-cast polycrystalline molybdenum of nominal purity 99.93+ pct and single-pass electron-beam zone-refined molybdenum single crystals having a nominal purity level of 99.99+ pct. The interstitial levels (weight percent) as determined by the Materials Testing Laboratories, Division of Magnaflux Corp., were as follows: sintered molybdenum (C— 0.005, H—0.0004, O—0.015, N—0.008); and arc-cast molybdenum (C-0.0038, H-0.0003, O-0.015, N-0.023). Single-crystal molybdenum obtained from Materials Research Corp. had a typical interstitial analysis of C-0.0015, H-0.00007, O—0.00045, and N-0.0001. Tensile specimens having a 5 mm diam by 50.8 mm length were prepared from these materials. An average grain diameter of 0.059 mm was obtained for the sintered specimens following a 4-hr, 1600°C heat treatment. Grain sizes from 0.019 to 0.149 mm were obtained in the arc-cast specimens following heat treatments from 1100° to 1600°C for 1 hr. This series of specimens was used exclusively for the grain-size effect studies. All samples were electrolytically polished in 97 pct sulfuric acid solution prior to testing. Experiments were performed at room temperature in an ion-pumped ultrahigh-vacuum system positioned in an Instron tensile machine, Fig. 1. A constant strain rate of 4.2 x 10-4 sec-1 as derived from crosshead displacement was assumed for the deformations. Starting vacuums ranged from 2 to 0.5 X 10-10 Torr. These pressure measurements were made using corrected values4 of an NRC Redhead gage. Comparative readings were also made against a G.E. triggered dis-

Jan 1, 1967