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By C. M. Wayman, R. Bullough

The selection rules fir twinning in fcc, bcc, and hcp lattices as established in Part I are used to predict the positions, relative to the matrix (untwinned) reciprocal lattice, of reflections due to double diffraction from the twins. These doubly diffracted reciprocal lattice points, which often coincide with ordinary matrix reciprocal lattice points, are deduced from kinematical considerations. 1. INTRODUCTION. A Bragg diffracted beam under certain conditions may be rediffracted to produce a third beam i .e., the incident beam, the first diffracted beam, and the rediffracted beam). In such a case an initial incident beam is diffracted by a set of planes; the diffracted beam may then be rediffracted by a second set of crystallographically different planes. The initially diffracted beam acts as an incident beam for the second set of planes, thus resulting in a twice-diffracted beam. This twice-diffracted beam may be regarded as a singly diffracted beam from a set of lattice planes whose structure factor is zero. In order to find the reciprocal lattice point corresponding to the doubly diffracted beam, it is customary1,2 to combine vectorially the component reciprocal lattice vectors which head to the extra reflections. For example, hcp metals may exhibit the forbidden (0001) reflections.* As Fig. 1 shows, the (0001) reciprocal lattice point results from: (1010) + (1011) = (0001) Similarly, combination of the beams (1011) and (1010) gives rise to: (1011)- (1010) = (0001) As Pashley and stowell2 have pointed out, even if in fact the double diffraction points lie on the Ewald sphere, they may not actually represent observed doubly diffracted beams because the initially diffracted primary beam, i.e., the source, must also correspond to a reciprocal lattice point which lies on the sphere of reflection; however, the reciprocal lattice point corresponding to the planes causing the rediffraction need not lie on the sphere. A little consideration of the Ewald construction in Fig. 2 makes this argument clear. In Fig. 2 the incident beam is represented by the wave vector ko. This beam is initially diffracted by the lattice planes (hkl) which are represented by the reciprocal lattice vector r(hk1) The reciprocal lattice point (hkl) of course lies on the Ewald sphere in order that the Bragg condition be satisfied. The initially diffracted beam is represented by the wave vector kl. If now kl is rediffracted by a second set of planes (h'k'l') resulting in k2 the lattice point (h"k"l") must lie on the Ewald sphere if the double diffracted beam k2 is to be observed. It is clear that (h"k"l") is the vector sum of (hkl) and (h'k'l'), and that (h'k'l') need not in fact lie on the Ewald sphere. In the usual1,2 analysis the origin (000) of the reciprocal lattice is shifted to the point (hkl). However the translation (000)— (hkl) automatically shifts the point (h'k'l') to the Ewald sphere, i.e., (h'k'l')— (h"k"1"). It is to be seen that (hkl), the source reflection, must lie on the Ewald sphere; if it does not the translation (000) — (hkl) places the "new" origin off the sphere, not satisfying the Ewald construction and hence the Bragg condition. The point (h"k"1") of course must lie on the sphere if it corresponds to an observed doubly diffracted beam. It is to be noted that crystals having the hcp structure, as just discussed, are intrinsically capable (i.e., without lattice defects such as twins) of double diffraction, as contrasted to fcc and bcc crystals which are extrinsically capable (requiring lattice defects or reoriented lattice regions). The "allowed" bcc reciprocal lattice points (which comprise an fcc lattice) are (110), (2001, (211), (220), (310), (2221, (321), (4001, and so forth. The combination

Jan 1, 1967

By G. Sachs, E. J. Ripling, J. J. Lynch

INTRODUCTION General IT is general practice to evaluate the strength properties of a particular metal from its stress-strain [(S1 - E1]) curve obtained by means of a conventional tension test. Such a stress-strain curve, Fig I, illustrates two important properties of a metal, its ability to strain harden, and its ability to withstand a certain limiting stress, the "fracture stress,"[ (s'r)], and a certain limiting strain, the "ductility" [(e1)], before it fails by separation. These two fracturing characteristics are the coordinates of the point of fracture in Fig I. In the case of a metal which necks in a tension test, both the fracture stress and the ductility (measured in a tension test) are dependent upon (a) the shape of the neck and (b) average values of the stresses and strains over the cross section at the moment of fracture. However, for the purpose of this investigation, these average quantities, rather than the actual values, may be considered for reasons of simplicity. It appears that the conclusions also hold true if the analysis were carried out for actual values of fracture stress and ductility at the locus of failure. In this paper, the effects of straining (at room temperature) by various methods on [ ] the above metal characteristics, which were determined by subsequent tension tests will be discussed. According to our present knowledge, any such prestraining results in a stress-strain curve (in subsequent testing by tension), Fig 2, the general shape, or flow characteristics, of which can be derived from the original stress-strain curve of the unstrained metal minus a certain portion exhausted by the initial straining. This phenomenon is called strain hardening, and may be measured by the magnitude of the cut-off, or the "effective strain," from which the new curve must start in order to coincide in its plastic branch with the original stress-strain curve.

Jan 1, 1948

By Howard Steven Strouth

The Blind River mining camp in Canada is all set to stage a major revolution. Enthusiasts on the scene say it will bring large-scale mining to North American uranium operation. If orebodies already discovered live up to their promise, it will be anything but the usual business of a few men handpicking orebearing rock out of small mines. Because of the geological structure of the region referred to generally as the Algoma district the ore may prove an extremely lucrative enterprise for years to come. The present center of activity is in Ontario about 75 miles east of Sault Ste. Marie, and just north of Lake Huron. It stacks up as one of the large uranium discoveries in the Western Hemisphere. For a change modern mining machinery working against large ore faces of predictable grade will enable mine operators to send a product to mills of several thousand tons daily capacity. Ore shapes-up as worth more than $20 per ton. Already, many millions of tons of ore have been outlined and apparently reserves are sufficient to keep the proposed large mills going for decades. And the end is not yet in sight. This region in the Sudbury subdivision has been known for decades as having occasionally rich but sporadic occurrences of nickel, gold, pyrite, and other minerals. Because of the unpredictable mineralization for more than 80 miles along the contact line of a huge reversed "S" there was no record of successfully organized mining in the district-until the present one.

Jan 5, 1955

By Arthur Winslow

Location.—The Liberty Bell gold-mine is in the San Juan region, in the southwestern corner of Colorado. It is situated about 2 miles from the town of Telluride, near the summit of the Uncompahgre range, at the head of Cornett basin, at an altitude of 11,000 feet, and in a district of excellent record in the past and of great promise for the future. In the immediate vicinity are such well-known and important mines as the Smuggler Union, with a total production of over $12,000,000; the Virginius and Revenue Tunnel group, with a production of probably $5,000,000; the Tom-Boy, with a production of probably at least $3,000,000; the Japan, the Cimarron, and a number of others. History.—The first prospecting in this district is reported to

Jan 1, 1900

By James Gayley

The occurrence of obstructions in furnace-hearths is nothing new to blast-furnace managers. The removal of them is becoming more and more simplified every day. The appliances that can be readily obtained at any works, are so simple in construction and effective in operation that they can overcome the most obstinate condition of affairs that can exist in a furnace-hearth. The old method of opening up tuyeres and notches with sledges and chipping-bass,. Was

Jan 1, 1886

By Oliver Bowles

While vast quantities of limestone and dolomite are used in metallurgy, the estimated production in 1926 being 23,860,000 tons, there are many problems connected with their use which have not received adequate study. The literature of metallurgy is notably lacking in comprehensive discussions of fluxing or furnace stone. Approximately 900 lb. of limestone is used for every long ton of pig iron produced in the blast furnace, but this important constituent of the charge receives little atten. tion compared with the intensive study that has been applied to ores and fuels, the other important constituents of the charge. In an effort to elucidate some of the doubtful points, the writer has made a wide review of metallurgical literature, and has had the disappointing experience of finding not more than a paragraph or two on metallurgical stone for each two or three thousand pages of literature reviewed. Furthermore, the limited information supplied is in some instances contradictory and even absurd. For example, a correspondent in a reputable metallurgical magazine classifies magnesia and silica together as impurities in flux " that must be melted and run off as slag." From the furnace operator's viewpoint it is desirable that as complete knowledge as possible be obtained concerning the effects of chemical composition and physical character of the stone on its action in the furnace and on the quality of the metal produced. A better knowledge of these features is advantageous also to the quarry operator in that it enables him to work more intelligently in producing stone that will best satisfy the metallurgists' requirements. The following pages comprise a brief compilation of data now available. Much of the information is well established and probably acceptable to most metallurgists. On some points there is room for debate, and the chief purpose in presenting a paper at this time is to arouse discussion which will throw more light on controversial points and thus assist the author in preparing a more comprehensive and accurate discussion of metallurgical limestone problems.

By F. C. Sturges

For some time mining engineers have been interested in the possibility of using small diameter shafts, sunk by core drilling, as aids to ventilation and as emergency escapeways. The possibilities are interesting to contemplate, but new methods involve unknowns, and interest tends to remain passive until these unknowns are, solved. Recently we have completed two 36-in. diam core drilled shafts, and wish to make the data on these available to the industry. Both shafts were drilled for the McLain Fire Brick Co., one at its Buckeye mine and the other at its Colonial mine. Both mines are in the fireclay underlying the Lower Kittanning coal. Both mines have been in operation for a number of years and have required expensive maintenance work on return airways. It was decided that considerable savings could be effected by short-circuiting the air to the surface through small shafts. It was also realized that these holes, located near the present workings, would be of added value as emergency escapeways. Originally, 48-in. diam shafts were considered, but actual computations showed 36-in. diam shafts were more than ample at both mines. The shaft at the Buckeye mine is 240 ft deep, and that at the Colonial mine 258 ft deep. Both holes were started in the lower part of the Conemaugh formation and penetrated Conemaugh and Allegheny strata. The holes were started through the unconsolidated materials overlying bedrock by constructing a concrete collar with a wall thickness of 8 in. Then the shafts were drilled by the shot-core drill method. An annular groove was cut in the rock by the abrading action of chilled steel shot run under the shoe of the core barrel. The drilling was done in stages, the core barrel drilling the groove for a certain distance depending on conditions encountered, and then the cores broken off and taken out in sections. The core barrel had a 36-in. o.d. and the finished diameter of the shaft measured almost 37 in. The major questions that could not be answered until the completion of the first shaft were, (I) how much ground water would be encountered, how would it hinder the drilling, and how difficult would it be to seal off, and, (2) how would the walls of the hole stand up. The holes of course could .be cased or lined, but that is considerable added expense in any shaft.

Jan 1, 1949

By Albert F. J. Bordeaux

(Cleveland Meeting, October, 1912.) THE immediate vicinity of the sea-shore, affording special facility for the exportation of ores, makes it possible to work certain mines in the Vladivostok district, which, in more remote places of Siberia, would remain unproductive. Outside of the city of Vladivostok the population is small and the country is very little prospected. Additional discoveries of valuable deposits like the large body of calamine which has recently been opened in the neighborhood of earlier worked lead-silver ores, in the Tetiuhe valley, are still in the field of possibilities. For many years gold alone was produced, in part from the coastal rivers and in part from a quartz-vein on Askold island near Vladivostok. But the production is diminishing, and prospectors are looking for other rivers in the interior, such as the tributaries of the Ussuri. These rivers are now more accessible than formerly, due to the slow but gradual development, of colonization by the Russian peasants. The few natives of the country, called Orodjones, are of the Chinese race. They resemble the North American Indian and are hardy fur-hunters. They have given some attention to placers and have already shown good specimens of gold-dust from the rivers Iman, Bikin, Noto, etc. Coal-mining was begun in the Vladivostok region more than 20 years ago, but in a somewhat irregular way. The industry is not as yet important and the best coal-seams are badly prospected, or ire even neglected. Copper, lead, and iron exist in several places. The amounts give some encouragement to the anticipation that the discoveries will give rise to important metallurgical works. I here present a review of the various deposits, based upon such safe information as is in hand, when I have not drawn upon my personal observations. Fig. 1 is a snap of Eastern Siberia, showing the mineral deposits.

Oct 1, 1912

By Robert L. Dean

THE pioneer mining company in Idaho to use airplanes extensively is the Yellow Pine project at Stibnite now owned by the Bradley interests. From 1901 to 1903 the gold boom at Thunder Mountain, in central Idaho overflowed to adjacent areas, prospectors discovering cinnabar and stibnite near the present site of Stibnite in Valley County. The workings were practically abandoned by 1911 through lack of capital and high costs of transportation on pack train roads over several mountain passes open only five months each year. During the World War there was some prospecting and production, and in 1921 twelve of the original companies were merged. Small-scale mining up to 1927 proved that an expenditure of several million dollars would be necessary to operate profitably. These properties were purchased by the Bradley interests during the period of 1927 to 1930. In 1927, there was no mining equipment except hand tools, no telephones, and only one building. Two mountain

Jan 1, 1935

By J. P. Dunlop

The fact is not.ablc though probably little known that thc Unitcd Statcls is the only nation obtaining and distributing through its Govcrn-ment burcaus any data pertaining to waste metals and drosses. Some foreign goverrlnlents do issuc reports relating to rnine or smelter production of prirrlar~ metals, but none gives in scope and detail t'he information published now by the U. S. Bureau of Mines and formerly by the U. S. Geological Survey; and this is despite the fact that the funds annually allotted for those purposes are insignificant in comparison with allotments for the preparation of data relating to other industries of like importance. The earliest data on the production of metals from secondary sources in the United States were contained in a press bulletin issued by the U. S. Geological Survey on Jan. 4, 1909. The information published was that for thc year 1907 obtained ant1 compiled by C. E. Siebenthal, who was one of the first to visualize the growing importance of the scrap-letal indust,ry. Thc Nationd Conscrvation Commission had emphasized its opinion that the known domestic supply of certain kinds of the morc important irietals was being rapidly marketed and that while there was no immediate cause for concern it was best to conserve such resources. Not only had there been a lanlentable lack of any data regarding the quantity of scrap inetals available or used but also gross carelessness and indifference in the segregation, collection, and effective use of scrap material. Siebenthal realized that even approximately correct statistics of recoveries from the more important base-metal scrap and drosses wcrc nearly as essential t,o both producers and consumers as the stat'istics of the output of primary metals. There were not then nor are there now sufficient funds for complete collection of data, nor was it considered the province of the Geological Survey t'o do more than determine approximately the recovery of secondary metals for use in supplementing those given for the primary metals. Undoubtedly the first bulletins issued did not give the full output, for it takes time to establish contacts for an inquiry covering so

By Auguste J. Rossi

We cannot expect, within the limits of this paper, to treat this subject exhaustively, but will endeavor, in the following, to present it in as concise a manner as is consistent with a clear exposition of its importance. Ores of titanium, titaniferous iron-ores (that is, iron-ores containing a notable amount of titanic acid, TiO2,, say not less than 5 per cent., generally 10 to 20 per cent., and frequently more, up to 40 per cent. or thereabout), occur all over the world in immense quantity, " in mountain masses," constituting in some localities, as in Sweden, Norway, Canada, the Adirondacks (N. Y.), in North Carolina and other States of the Union, the geological formation itself, the igneous rocks having, in many places, been so permeated with the metallic oxides as to justify their being called iron-ores. As a rule they are Bessemer ores, quite free from phosphorus and sulphur, though not invariably so. When the percentage of titanic acid is very high, that of the iron is low, but the proportions do not necessarily vary in the same ratio; that is, a rich ore may contain more titanic acid than one lower in iron. The percentage of iron varies, being as low as 35 to 36 per cent. in real ilmenite. It is more generally not less than 50 to 55 per cent., reaching often an average of 58 to 60 per cent., and as high as 63 to 65 per cent. It is obvious that if these ores were to be considered in the same light as other iron-ores, equally rich in iron, they would form an excellent stock for blast-furnaces for years to come, as their supply might be called inexhaustible, and they could

Jan 1, 1903

By C. F. Cornell, R. C. Emmett, D. A. Dahlstrom

FOR many years the disk-type and cloth-covered drum filters have found widest application in liquid-solids separation, which uses continuous filters. The disk type is less expensive, occupies less floor space per square foot of filtration area, and re- quires negligible down time for filter media changing. However, because filter cloth is billowed out by the blowback in the cake discharge, it is very short-lived if the scraper blades are set too close. Consequently cake weight is very important in assisting cake discharge, which normally necessitates a minimum cake thickness of 3/8 to ½ in. Also, the vertical position of the disks eliminates the possibility of efficient cake washing for removal of soluble values. The disk-type filter is generally limited, therefore, to applications that require no cake washing and form relatively thick cakes within the normal range of filter cycle times. The conventional cloth-covered drum filter is a more flexible unit, permitting wider variation in the percentage of cycle time devoted to cake formation, dewatering, or washing, as required by the application. Thinner filter cakes can be discharged be- cause a horizontal line across the filter medium at the location of the scraper blade is equidistant from the edge of the blade at all points. The scraper blade therefore may be set a short distance from the filter medium or, where wire winding is not used, a floating scraper can be utilized so that the contour of the cloth can be followed. The drum filter is generally employed when there are difficult filtering slurries with resultant thin cakes or when cake washing to recover soluble values must be practiced.

Jan 2, 1958

By Theo W. Robinson

The evolution of the modern blast-furnace from the embryonic stages of comparatively few years ago, has been the work of wide praetiee and experiment. That much is still to be desired, the experience of every furnace-manager mill testify. Mr. Walsh's paper on "The Irregularities of the Blast-Furnace Process, and a Practical Way to Avoid Them" (Trans., xv., 419), proposes a new solution of the problem of interior lines, and one that has given rise to not a little speculation and controversy. The investigation described in this paper was undertaken to test experimentally the theory of Mr. Walsh as to maximum reducing capacity. Briefly explained, Mr. Walsh's views (outside of his claim for increased efficiency due to having the bosh wholly within the meltingzone) are, that a furnace of contracted stack and throat, on his lines. may equal in product one of considerably greater cubical capacity. The explanation offered for the theoretical greater capacity per cubic foot of his furnace is, that the increased tension of gases caused by passing through the small area mill promote transpiration, thus facilitating reduction and permitting more rapid driving. This alleged relation will appear from a hypothetical case in which a furnace, A, constructed on Mr. Walsh's lines, has but 1/x of the cubical contents of a furnace, B, of modern type; the two being equal in height. In order that A shall have the same capacity as B, both working normally with the same mixture and burden, and

Jan 1, 1889

[ZAY JEFFRRIES, Vice-chairman PAUL D, MERICA, Chairman W, M, CORSE, Secretary Executive Committee J. It, FREEMAN, JR., Local Section S. SKOWRONSKI, Papers Committee R. S, ARCHER, Non-ferrous Data Sheets H, C, JENNISON, Membership Committee E, C, BAIN, Journal Committee L, W. SPRING Local Section Committee J. R, FREEMAN, JR,, Chairman R. J, ANDERSON, Cincinnati R. L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G, H, CLAMER, Philadelphia W. A. SCHEUCH, Chicago R, F, WOOD, New York]

Jan 1, 1928

By Freeman Bishop

The Bureau of Mines is working on a long-term program to completely revolutionize mining-to create a mine-systems technology that integrates the need to recover minerals at low cost under safe and healthful working conditions while protecting the environment. Everyone should be brought into the planning process preceding each new mining development, the Interior Department urges, and Assistant Secretary Hollis M. Dole seems determined to push this kind of systems approach with everything he can move.

Jan 1, 1970

By John V. W. Reynders

Our entry into the World War suddenly brought home to us in a startling way the vital importance of manganese. Since the war, much has been written and said upon the subject of manganese and a great deal of time and money have been spent in attempts to find an adequate substitute for this metal in the manufacture of steel; none has been found. It is true that ways are known by which it is possible to make small amounts of good steel without manganese, but taking into consideration the diminishing quality of iron ores and fuels as well as the increasing exaction of specifications for finished products, it may safely be assumed that, high-grade manganese ore will be more and more a necessity in the production of steel as time goes on. Taking world resources as a whole it may be well to point out that the problem of obtaining needed supplies of manganese from a strictly commercial viewpoint is now less serious than it was before the war. Formerly it was feared that world resources of high-grade manganese ore might be exhausted in a relatively short time, but, largely as a result of the stress laid upon the importance of manganese during the war, the world's available supply of high-grade manganese ore has been greatly augmented by new discoveries and fuller development of previously known deposits. Sources of Production Russia alone, of countries producing the major part of the world's stee1, has within its geographical boundaries sufficient manganese to supply its needs. The domestic production of England is inadequate and English requirements for high-grade manganese are supplied principally from India. France also draws largely upon India, as it depends upon foreign sources of supply except with respect to a small tonnage of silico-manga-nese and silico-spiegel produced in the Hautes-Pyrénées. Germany and the United States likewise depend upon foreign sources of high-grade ore, though each possesses comparatively large reserves of ferruginous manganese ore and manganiferous iron ore. At present the world demand for high-grade manganese ore is met with ease by the production of Russia, India, Gold Coast and Brazil.

Jan 1, 1927

By C. S. Smith, W. M. Williams

THE quantitative study of grain shape in three dimensions has been a difficult one from the practical standpoint. Experiments on grain shape have usually been based on indirect observations of two-dimensional metallographic samples or on grains separated by intergranular corrosion or fracture. The latter method was used in particular by Deschl in 1919 in observing the shapes of ß-brass grains which had been separated with mercury. The similarity in detail of shape and packing that exists between bubbles in a soap froth and metal grains was noted by Desch who remarks that: "Surface tension has an. important share in determining the form of the crystal grains in a solidifying metal and such grains have a tendency to assume the shape of foam cells." More recently the relation between grain shape and grain growth has been studied by Harker and Parker.' The importance of surface tension forces in determining microstructure has been discussed by Smith," and an analysis of the topologi-cal rules that apply to such structures has been made by the same author.' Biologists have made valuable contributions to the general problem of shape and form in an assembly of space-filling cells subject to surface tension forces. Particular mention must be made of the extensive researches of Lewis5,8 on botanical and anatomical tissues, and Matzke and Nestler,7,8 who have made painstaking studies of bubble shapes in different kinds of foam. The present paper introduces a new method of studying individual grains in particular alloys—a method which may well find use in other metallurgical researches, and which seems also to be applicable in biological problems. Metal Grains in Three Dimensions The individual grains in a piece of metal or the bubbles in a soap froth must satisfy two conditions —they must be in juxtaposition so as to fill space and their interfaces must conform to the laws of surface tension. If a further restriction is imposed, namely, that only one type of polyhedron be used, then the sole possibility is an assembly of "minimal" tetrakaidecahedra," each polyhedron having eight doubly-curved hexagonal faces and six plane quadrilateral faces, the angles between adjacent faces being 120". Such cells could be stacked on a body-centered cubic lattice and would be quite stable. For many years it was believed that soap bubbles actually possessed the shape of this ideal body, and the hypothesis was the starting point for several investigations on the shapes of soap bubbles, biological cells, and metal grains. These investigations have shown, what might have been obvious in the beginning, that if the condition of symmetry is relaxed the tetrakaidecahedron is almost never found. If we retain only the rule that all contacts should be in local surface tension equilibrium and that the assembly should fill space, metal grains may then take a nearly infinite variety of shapes and no single one may be regarded as an archetype. These two conditions, which are fully discussed in one of the previously mentioned papers,' lead us to think of a typical grain in an annealed metal as having the following characteristics: 1—A grain may have any number of faces, but usually between nine and eighteen. The faces (each of which is, of course, shared by two grains in the assembly) may have any number of edges, but usually between four and six. Pentagons are by far the most frequent. 2—In the assembly of grains each edge is shared by three faces and by three grains. Each vertex is a point shared by four grains, six faces, and four

Jan 1, 1953

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By George Moore

IN spite of many investigations of the occlusion of hydrogen in iron, the nature of the process and the reasons for the accompanying effects upon the metal are still open questions. This is in large part due to three causes: (1) the difficulty of obtaining iron of adequate purity as starting material; (2) the occurrence of allotropic transformations, which compli-cate the effects; and (3) the fact that the body-centered cubic modifica-tion does not lend itself readily to crystallographic investigation. The present paper attempts a critical review and correlation of the somewhat scattered and disconnected existing observations, and an experimental determination of the extent to which the conclusions that appear to follow from these are applicable to iron of really high purity, studied under well-defined conditions.

Jan 1, 1939

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967