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By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By R. L. Fleischer, B. Chalmers

In order to observe size effects associated with a grain boundary, aluminum single crystals and bicrystals of various cross-sectional dimensions were deformed in tension. Typical stress-strain curves are presented in conjunction with measurements of the effects of changes in crystal dimensions. Some effects of the growth rate used in preparation of crystals are also described. It is indicated that the macroscopic constraints at a grain boundary are responsible for the most prominent grain-boundary effect, the production of multiple slip. Two measurements of the width of the region of double slip are in agreement. It is concluded that the yield stress of aluminum is affected markedly by the inherent oxide coating. THE general problem to be examined is that of dimensional effects in the plastic deformation of metal crystals. These effects will be termed "size effects" and are here defined as follows: A size effect occurs in a series of crystals if their plastic-deformation properties are a function of crystal dimensions. Clearly then size effects depend on the nature of the boundary conditions imposed on the crystal. Crystal boundaries can be of three types: interphase, inter-crystalline, and free surface. Such deformation effects as are caused by distribution of phases, grain size, lineage structure, and single crystal external geometry are specific types of size effects. This discussion will be confined primarily to grain-boundary and single-crystal size effects, though in practice most "single crystals" not only have a number of small angle boundaries but also have one or more surface phases, so that the boundary conditions appropriate to a free surface do not necessarily apply. Hence, to this extent interphase size effects will be considered. The question of size effects associated with grain boundaries (called here intercrystalline size effects)

Jan 1, 1959

By J. L. Whitlock

An attached growth aerobic biological treatment process has been developed at Homestake Mining Co.'s Lead operation which not only oxidizes free and complexed cyanides, including the stable iron complexed cyanides, but also thiocyanate, and the oxidation byproduct ammonia. Through the employment of a mutant strain of bacteria which has been gradually and specifically acclimated to the waste, these potential pollutants are mineralized to relatively harmless sulfates, carbonates, and nitrates. The resultant effluent, through toxicological testing, has been shown compatible with the receiving stream, which serves as a cold water marginal trout fishery.

Jan 1, 1985

By B. G. Klugh

(New York Meeting, February, 1913.) THE present paper represents a preliminary investigation of the ultimate structure of iron-bearing materials which have been subjected to heat treatment for the purpose of agglormer-ating the fines, or for chemical changes, or for both. Primarily, the object of this inquiry was to determine the relation of the microstructure of each of these materials-to its specific susceptibility to the action in the blast-furnace. It is hoped that this small contribution will serve as a nucleus to a line of research that will throw some light upon the debated questions involved in blast-roasting. Thus far the investigation has been conducted along lines of analogy of known principles, rather than through the applica-tion of any well-defined system of microscopic petrography. This is obviously due to the fact that we are dealing with materials which are the artificial products of a new art, rather than with the natural materials from which the essence of the pure science has been evolved. In the limited tune allowed for this research, it has been conducted upon those materials the chemical content of which allows of their use commercially in the blast-furnace.

Jan 5, 1913

By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By J. L. Walter

Tungsten ingots with and without small amounts of aluminum, silicon, and potassium were prepared by conventional powder-metallurgy techniques and hot-rolled to 0.001-in.-thick sheet. The ingots were rolled three different ways: I) initially cross-rolled, then straight-rolled; 2) straight-rolled, and 3) straig-ht-rolled, then cross-rolled. Total reductions were 99.8 pct. Samples of the sheet were annealed, in vacuo, at temperatures from 1200" to 2200°C. Substructures and textures were determined by transmission electron microscopy and X-ray diffraction. The doping agents were found to form particles of mullite (Al,Si,O,,) which, on rolling., appear to form strings of particles aligned parallel to the rolling direction. These strings of purticles are associated with an increase in the recrystal-lizution temperature from 1400°C for undoped sheet ThE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of drawn and recrystallized wire.'" The grains generally do not occupy the entire cross section of the wire and have lengths many times the wire diameter. The grain boundaries are, in general, nearly parallel to the wire axis and have long ''fingers" projecting one into the other as may be seen in Fig. 1, a longitudinal section of recrystallized doped wire. When unsuitable additions or no additions are made or the wire is not sufficiently reduced during draw- to 2000°C for doped sheet. The particles also limit lateral grain growth while allowing growth parallel to the rolling direction. This results in the formation by primary re crystallization of large highly elongated grains of specific preferred orientation. The undoped sheet recrystallized to small equiaxed gains. The preferred orientations of the large grains were determined from axis density plots to be (113) (691). (0i3) (362), (116) (304) types for the initially cross-rolled then straight rolled material. These orientations are similar to the orientations of the large elongated grains in doped and heavily drawn tungsten wire. The nucleation of the large grains appears to occur by recovery of certain of the polygonized regions of specific orientation, followed by strain-induced boundary migration.

Jan 1, 1968

THE Copperton mill in reality was a sort of proving ground. It was. designed to serve three purposes: (1) to verify the accuracy of the mine sampling by actually treating substantial tonnages of ore, (2) to demonstrate on a reasonably large scale the percentage of the copper in the ore that could be recovered, and (3) to permit the testing of various kinds of machines and devices for crushing and concentrating the ore, so as to guide the engineers in designing the proposed 6000-ton milling plant at Garfield. As a matter of fact, it contained a lot of second-hand equipment sent by MacNeill and Penrose from the works of the United States Reduction &Refining Co. in Colorado; and it was by no means a model installation. Probably it would have been even less efficient, except for the skillful work of George O. Bradley and-Frank-G, Janney, both of whom had worked with Jackling at Mercur. Bradley was a mechanical engineer employed to design the plant. Later he directed the design of the concentrator at Garfield and remained as consulting mechanical engineer to the company until 1915. Janney, who afterwards became manager of mills, a position that he retained until his death in 1916, was a skilled mechanic at the Golden Gate mill at Mercur when Jackling built the plant in 1897. His flair was making machinery do what it was intended to do. He was not an ore-dressing engineer in a technical sense; but Jackling him- self was a specialist in this respect as well as in designing and construction and Janney's mechanical aptitude made him a particularly valuable man in the Utah organization. John McDonald, another of Jackling's Mercur associates, was the first mine superintendent. With practically all of the available funds earmarked for construction of the Copperton

Jan 1, 1933

By B. F. Fackenthall

The Durham Iron Works of Messrs. Cooper & Hewitt, near Riegelsville, Pa., occupy a site which has been almost continuously the scene of iron-manufacturing industry since 1727. Doubtless if Anthony Morris and his thirteen associates, who in that year erected a blast-furnace on the Durham Creek, a short distance above where the Durham Iron Works now stands, could have had a vision of the improved and enlarged apparatus of their successors, they would have been not less astonished by the huge stack, the hot-blast ovens, and the blowing-engines of the modern blast-furnace, than by the railroad which now follows the bank of the river on which their clumsy " Durham boats " once floated pig-iron to Philadelphia. In one particular, posterity must confess their snperiority. We are told that in November, 1728, they shipped three tons of Durham iron to England. The proprietors of the Durham Iron Works are not now shipping iron to England. The present Durham furnace was built (in place of two smaller ones) in 1874 and 1875, and made its first blast in 1876. A description of it, with other works of the same proprietors, at Trenton, N. J., by A. L. Holley and Lenox Smith, was published in London Engineering for January 31st, and February 21st, 1879. Since that time, a number of improvements, dictated by experience, have been made in the details of the furnace and fittings; and the recent roilclusion of a long and successful blast presents a convenient opportunity for a description of the works and a statement of the results of practice. The accompanying drawings will show the general arrangement of the works. The furnace, Plate I., Figs. 1 and 2, is 75 feet high by 19 feet bosh. The hearth is 11 feet 4 inches in diameter, with seven tuyeres 5 feet 6 inches above hearth-line. The tuyeres project 9 inches into the furnace, making the interior tuyere-circle 9 feet 10 inches in diameter. The front is a modification of Luermaun's

Jan 1, 1886

By Edmund C. Pechin

THE writer approaches this subject with a great deal of diffidence —first, because it is utterly impossible to treat it satisfactorily within the limits of a paper, and, secondly, because the larger development is of so comparatively a recent date as to make authoritative data on some interesting points unavailable. For over one hundred years small charcoal-fnrnaces have been in existence, at widely scattered points, making a few tons of iron daily, and then gradually increasing to a daily output of, say 10 to 12 tons, as the market widened. With the exhaustion of local supplies of wood, inaccessibility to market, and sharp competition, bringing lower prices, many were compelled from time to time to make temporary stops, and finally to cease altogether. During the first half of the century there were at different times in operation between 75 and 90 charcoal furnaces. The last Directory of the Iron and Steel Works of the United States (1890) gives 19 as the number of charcoal-stacks in Virginia. Of these several are cold, and, it is

Jan 1, 1891

By N. F. Mott

Jan 1, 1961

By R. F. Mehl, J. T. Ransom

For many years the Metals Research Laboratory of Carnegie Institute of Technology has been concerned with the statistical nature of the engineering properties of steel from an experimental viewpoint, particularly those properties representing ductility.' In the past three years new work has been directed toward evaluating the statistical nature of the endurance properties. It has been shown that both the fracture curve and the endurance limit in fatigue are markedly statistical in nature. The S-N curve (and the endurance limit) of ferrous materials is often determined with specimens which number as few as ten. The common procedure is to test the first specimen at a stress well above the expected endurance hmit. Each succeeding specimen is then tested at a progressively lower stress, until, after five or six tests, a specimen runs ten million or so cycles without failing. Two or three more specimens are then used to find the highest stress at which failure will not occur; the limiting stress determined in this way is called the endurance limit. It has now been found, however, that the variability in the fracture curve and in the endurance limit in heat-treated alloy forging steels is so great that S-N curves must be drawn on the basis of distribution curves which can be appraised only by statistical methods. Two methods have been adopted in this study: (1) straightforward statistical studies of cycles to fracture of a number of specimens at each of a series of stress levels, and (2) a new abbreviated statistical method, known as "staircase testing."2 The latter corisists in testing a series of specimens, one by one, with the test stress for any given specimen automatically

Jan 1, 1950

By B. M. Blake, R. S. Reppert, A. F. Keiser, E. J. Trinkle

The southern West Virginia coalfield was formed in a rapidly subsiding depositional basin associated with deep-seated growth faults. Subsidence began to the southeast during deposition of the Pocahontas Formation, and then shifted to the northwest during deposition of the New River, Kanawha, and Allegheny Formations. Rocks of all the coal-bearing formations grade into massive sandstones to the northwest. For the No. 3 Pocahontas, Sewell, Campbells Creek, and No. 5 Block coals discussed in this study, the overall sulfur and ash values of each coal seam increase gradually toward the northwest. The thickness of each coal tends to increase toward the southeast. These trends are partly a reflection of the differential subsidence of the coal basin along with varying degrees of peat accumulation and degradation. The northwest side of the coal swamps underwent relatively less subsidence and, thus, more degradation due to increased aerial exposure, with a resulting increase in the sulfur and ash values of the coals, and a decrease in the thickness. The open sea existed to the west of the coal swamps, and this marine environment also contributed to the higher sulfur values to the northwest. Coals of the Pottsville Group in the southern West Virginia coalfield generally have sulfur values between 0.6-1.0% with some as high as 2-3% on the northwest edge of the coal basin.

Jan 1, 1983

By F. W. SUTTER

IN order to have ore available on the completion of the beneficiation plant at Clifton and to provide for continuous production while underground development was carried out, it was decided to develop an open-pit through the crest of a long hill in which the ore outcropped, using 40-ft. vertical benches.

Jan 1, 1943

By C. Hanford Henderson

The belt of copper-bearing rocks of the South Mountain has attracted Attention principally iii the townships of Hamilton Ban and Liberty in Adams County, Pennsylvania, and in the southeastern portion of Franklin County. As the developments, thus far, have been almost exclusively limited to that area, the examination here described extended only within those boundaries. The region, being one of considerable interest geologically, has been the subject of careful study and description, both on the part

Jan 1, 1884

By Charles P. Williams

The lead-bearing area of Missouri has been subdivided, geographically, into the Southeastern, the Central, and the Southwestern

By R. M. Brick, Arthur Phillips, A. J. Smith

A PREVIOUS publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuA12. A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation. to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic deformation or cracking has been considered in relation to the physical properties of the alloy. On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degree of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. STRAIN IN SOLID-SOLUTION ALLOYS A 10 per cent magnesium alloy in the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using aluminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl2, CaC12, NaCl. Chill-cast rods were sealed under vacuum

Jan 1, 1935

By R. F. Domagala, M. Hansen, D. J. McPherson

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957

By Albert J. Phillips

As early as 1824, Haidinger' described crystals of native copper that were, according to Dana,2 " probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

By Sidney Powers

INTRODUCTION THIS paper aims to present the results of an investigation concerning gravitative differentiation in lava flows, based on a quantitative microscopic and chemical study of a Triassic basalt from Nova Scotia, and confirmed by data secured from a study of certain Keweenawan ophites. At Cape d'Or, Nova Scotia, near the head of the Bay of Fundy, marine erosion has exposed a series of Triassic basalt flows in which copper has been sought for a number of years. Studies of the thickest flow of the series with regard to volumetric composition, specific gravity, and grain have been made by the junior author, and measurements by students at Tufts College, together with confirmatory observations of the same nature on this and other flows by the senior writer, and chemical analyses made by the Division of Mines, Mines Branch, Ottawa,1 all show differentiation in lava flows comparable to that in intrusive bodies. The work was made possible by the availability of the drill-cores, the property of Tufts College, and emphasizes the desirability of the study of drill-cores from other localities. Measurements of the specific gravities of certain Keweenawan lava flows of -Michigan by the senior author, from material collected in 1915, will be given as a comparison to those of the Cape d'Or flow. It has been found that the specific gravity of drill-cores, or volume per cubic foot, can be readily obtained by measuring their dimensions. This can be done to an accuracy of within 1 per cent. in pieces of core over 100 min. in length by using a micrometer gage for the diameter, and taking the average of six measurements of the diameter; and the average of four measurements of the length made with a finely graduated ruler. Then, after weighing them, the weight in grains per cubic centimeter, or what is practically the same thing, ounces per cubic foot, is obtained. System-

Jan 2, 1916