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By H. F. Silliman, Daniel R. Hull, Earl W. Palmer

THE brass-rolling industry has not had a great deal of experience with antimony in its product. There have been some recent excursions with antimony as a corrosion inhibitor in tubes, but in sheet brass it has been regarded with apprehension and generally avoided. This is not to say that [ ] contaminations have never occurred, and probably a great many brass mill men have had their own ideas on the effect of such contamination. Our own views were based upon certain experiences some years ago with strip castings that split lengthwise in the early stages of rolling. The nature of this splitting is shown in Fig. I, from a photograph taken in 1922 as a record of 20 bars of 65-35 common brass made with an antimonial brand of copper. These bars were cast 6 ¾ in. wide by 1 in. thick by 45 in. long. In the first pass through the rolls, 19 of the 20 split lengthwise throughout their length, while each half curved outward in a wide arc as it emerged from the rolls. [ ] In those days, if splitting was not a frequent occurrence, it was not unfamiliar. One can recall periods of short duration when large amounts of common brass would behave in this way. There was nothing imaginary about these spells. The affected metal would split lengthwise in the breaking rolls, and no maneuvering of mill practice made any difference. The condition would descend like a plague, demoralize the mill for several days, and disappear. It is doubtful if anyone knew the cause-however many explanations may have been current. In 1921 a quantity of split brass was traced to the use of fired small-arms

Jan 1, 1943

By E. F. Koppe

The Upper Freeport coal in the Freeport and New Kensington quadrangles, Pennsylvania, varies from a bony streak to a thick coal deposit often exceeding ninety inches, the "Double" or "Thick Freeport". Distinctive basal partings, a central bone layer, and a canneloid top bench may be present. The appearance of a sandstone roof, sandstone rolls, and bony coal at the top of the main coal bench can be anticipated in thin Freeport areas when basal partings are absent. When the two basal partings are present, a shale roof is normal. These effects are correlated with the original topography upon which the coal was deposited. The original depositional high areas tend to coincide with present structural highs. Preliminary data indicate that coal quality, in part, is affected by the deposi-tional setting. In "high" areas, a tendency exists for the main coal bench to contain higher percentages of fusain and mineral matter. Within limits, some-what higher ash fusion temperatures appear to correlate with paleotopographic highs. As a result of these findings, critical examination of the paleotopography and related sediments is indicated in other areas and other coals. The Upper Freeport coal is quite variable both in thickness and composition in the Freeport and New Kensington quadrangles of Pennsylvania (Figure 1). The coal horizon in these quadrangles is marked either by a thin carbonaceous shale bed or by a single bed containing a variable number of partings (binders). The complex coal zone known locally as the "Double" or "Thick Freeport" contains the Upper Freeport Coal Bed at the base; but in addition, it has an overlying bone layer and an upper coal bed occasionally capped with a canneloid layer. The "Thick Freeport" often exceeds 90 inches in thickness, whereas the normal Upper Freeport coal usually varies between 34 and 50 inches.

Jan 1, 1961

By FRANK R. VAN

I. INTRODUCTION. IN the summer of 1908, R. B. Cochran, Superintendent of the Compania Metalurgica Mexicana at Sierra Mojada, Mexico, presented to the Department of Geology and Mineralogy at Case School of Applied Science an interesting series of silver-, copper-, and lead-ores from the Veta Rica mine. These ores contained several interesting minerals which were associated in a somewhat peculiar manner, so that I was impelled to make a closer study of their occurrence. The investigation has brought out several new facts concerning the geology of the district and the geological occurrence of the ores, and therefore has seemed worthy of record. Two papers have been published previously about the region, one by Chism1 in 1887, and the other by Malcolmson2 in 1902. These articles, however, treat of the district more from the stand-point of the metallurgist and mining engineer, and not much attention is devoted to its mineralogy and economic geology. II. GEOGRAPHICAL LOCATION OF THE DISTRICT. The Sierra Mojada is situated in the extreme western part of the State of Coahuila, near the Chihuahua boundary. It is reached best via the Mexican Central railroad from El Paso, Tex., to Escalon, Chihuahua, a distance of 494 miles. From this point, a branch line, the Mexican Northern railroad, runs 78 miles in a NE. direction to the mines, which are its northern terminus. The railroad was built about 1890, practically on account of the Sierra Mojada mining-district. 1 Sierra Mojada, Mexico, by Richard E. Chism, Trans., xv., 542 (1886-87). 2 The Sierra Mojada, Coahuila, Mexico, and Its Ore-Deposits, by James W. Malcomson, Tram., xxxii., 100 (1901).

Aug 1, 1912

By J. H. Jackson, J. G. Kura, M. C. Udy, L. W. Eastwood

The melting and casting of any commercial metal depends upon the success with which the problems attendant to the handling of the specific metal are overcome. Common difficulties encountered in the handling of commercial metals are tendencies to burn or oxidize excessively, low fluidity, entrapment of dross, hot cracking, cold embrittlement, cold shuts, and un-soundness caused by gas evolution. Beryllium is not only subject to these same difficulties but is generally more sensitive to them than are the more common metals, thus necessitating more exact founding precautions. Characteristics of Beryllium Certain characteristics of beryllium which make it particularly difficult to handle in the plant or laboratory are as follows: 1. The melting point of beryllium is about 2400°F and pouring temperatures vary from 2600 to 2900°F, depending upon the degree of fluidity required. The extreme chemical activity, combined with the high temperatures, makes necessary the use of inert atmospheres, slags, or vacuum for protection during melting and pouring. Furthermore, beryllium tends to react with the melting crucibles, tools, and molds, thus requiring the selection of suitable materials and proper maintenance of these items. 2. The very marked absorption of gas by molten beryllium and the subsequent evolution of gas during solidification causes a great deal of difficulty with unsoundness. Beryllium castings may also be subject to unsoundness as a result of gas formation by chemical reaction with the mold surface during solidification. 3. The very marked chemical affinity between molten beryllium and the normal atmosphere causes the formation of dross. On relatively quiescent melts, this dross forms a very tenacious film which, if carried over to the mold, can cause defects such as the formation of skins or dross in the interior or on the surface of the casting; folds or defects similar to cold shuts may also be found. 4. During the pour and attendant turbulence, the dross may be mixed into the metal and then carried to the casting. There it may be entrapped during freezing and cause internal defects, or it may float to the surface and cause severe dross defects on the cope side of the castings. 5. Solid beryllium is very weak at a temperature near the solidus line; brittleness is also a problem at lower temperatures. Thus, hot and cold cracking must be guarded against. Scope of the Experimental Work All of these problems have been given consideration in the work at Battelle. Before the work was started at Battelle, it was customary to melt beryllium in a vacuum furnace or under flux in graphite-lined induction furnaces. Because of the difficulty of preventing gas unsoundness in beryllium castings, an investigation was undertaken primarily to study this particular problem and, secondarily, to devise methods of overcoming the other difficulties encountered in the founding of beryllium. The objectives of the laboratory work were multifold: 1. To devise a practical method of melting, other than vacuum melting, by means of which consistently sound beryllium castings could be produced. 2. To obtain fundamental data which would promote a better understanding of the causes of gas unsoundness in beryllium. 3. To develop a casting technique which would permit low melt temperatures, minimize dross defects and hot cracking, and eliminate reaction with the mold surface. Up to the present time, a considerable amount of progress has been made on the first and third objectives, with the result that it can now be safely stated that consistently sound castings can be made by the open-pot melting method, using argon as a protective atmosphere and a proper casting technique. There has been some progress on the second objective of the project, but it cannot yet be safely stated that the problem is completely understood. Most of the experimental work has been conducted in an enclosed melting and pouring apparatus in which very-close control of melting variables has been effected. Findings based on the results of the work conducted in this small experimental apparatus have been applied to large-scale melts which have been made by techniques suitable for duplication on a commercial scale.

Jan 1, 1950

By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By R. T. Hukki

THE accepted basis of comparisons between mills of different diameter is the percentage critical speed. If n = actual mill speed, rpm, nc = calculated critical speed, rpm, np = calculated percentage critical speed, and D == inside diameter of the mill in feet, then n, In the following analysis capacity, T, is expressed in short tons per hour, tph, and power consumption, P, in kilowatts, kw. Accordingly power consumption per unit of capacity, P will be expressed in kilowatt hours per short ton, or kw-hr per ton. In all equations D refers to the inside diameter of the mill in feet and v to the peripheral speed of the mill in feet per minute inside the liners. ' Comparison between separate mills must be based on equivalent grinding conditions, i.e., same feed, same size distribution of feed, same size distribution of product, and same percentage of solids. In addition, comparisons between separate rod mills must be based on the same rods, same type of liners, and same percentage rod load. Comparisons between separate ball mills presuppose the same balls, similar liners, and same relative ball load. The practical np-range through which the equations apply varies, being narrower for fine grinding in ball mills and wider for coarse crushing in rod mills. The Relationship between Capacity and Speed It is the general belief that the capacity, T, of a tumbling mill is directly proportional to the speed of the mill, other things remaining constant.' Mathematically this is represented by the equation T - c¹ n tph [4] where c, is a factor related with the grinding characteristics of the ore, method of reduction, and the units chosen. It is proposed here that the general equation relating mill capacity and speed should be of the form T = c¹ nm tph [5] In other words, the capacity should be proportional to the mill speed raised to power m, the numerical value of the exponent being 1 5 m 5 1.5, depending on the circumstances. Eq. 5 can also be written in the following forms: T = c, (np)m tph, and [6] T=Ca vm tph, [71 where v = peripheral speed of the mill in feet per minute. If the observed capacity of a mill at speed n¹ is = T¹ tph, the capacity T² of the same mill at speed n² should be T² = T¹ (n²/n¹)tph [8] The Relationship between Power Consumption, Mill Diameter, and Speed The only well known theoretical deduction relating power consumption, P, and mill diameter appears to be the formula of duPont introduced by Gow, Guggenheim, Campbell, and Coghill.' According to duPont, the power required to operate a mill is a function of the mass of the balls, of the lever arm of the ball mass, and of the speed of the mill. The ball mass per unit of mill length is proportional to the square of the diameter, the lever arm is directly proportional to the diameter, and the critical mill speed or any percentage thereof is inversely proportional to the square root of the mill diameter. Following this reasoning, the original duPont formula is of the form P = c4D² c D • c6D-0.5 = c7D2.5 [9] If the mill speed in the above equation is expressed in terms of Eq. 3, the duPont formula may be written as follows: P=f1(D2) f2(D) f³(—np) or [10] vD P = c np D2.5 kw [11] Eq. 11 may also be derived from the mechanical principle of force, which is equal to mass x acceleration. Power necessary to operate a mill may be considered to be an homogeneous linear function of the force developed. Ball or rod mass per unit of mill length is a function of D2. The acceleration factor of the ball or rod mass is a function of the peripheral speed of the mill. Thus P = f4(F) = /x(D2) f5(v) Indicating that v = nDn, and n = c9 np /vD, the above equation becomes P = f2 (D2) -fa (D ca np/vD

Jan 1, 1955

By Arnulf Muan, W. C. Hahn

Activities of "FeO" in "FeO"-MgO solid solutions have been determined in the temperature interval 1100" to 1300"C by equilibrating oxide samples with pure metallic iron in atmospheres of known oxygen partial pressures. The end members "FeO" and MgO form a complete solid solution series. The system shoztls a considerable positive deviation from Raoult's law. A large amount of data has been accumulated during the past 50 years on stability relations existing among various crystalline and liquid phases in oxide systems of importance in metallurgical processes. By comparison, very little is known about the thermodynamic properties within the various homogeneous phases present in the systems, particularly the crystalline phases. The present paper deals with determination of activities as a function of composition in solid solutions of wüstite ("FeO") and periclase (MgO). Such solid solutions ("Magnesiowustites") have simple sodium chloride structure and are known to be continuous between the end members at elevated temperatures (> 1000°C) and strongly reducing conditions such as prevail in contact with metallic iron. Wiistite has a defect structure in which the ratio of oxygen to iron varies and never has as low a value as 1:1 corresponding to the simplified formula FeO. Within the range of stability of this phase, the composition changes between a maximum oxygen content of approximately 25.6 wt pct (corresponding to the formula FeO.83O) and a minimum oxygen content of approximately 23.2 wt pct (corresponding to the formula Fe0-96O). The activity data to be reported in the present paper are based on using as standard state the wüstite which is in equilibrium with metallic iron at a particular temperature, i.e., "FeO" of minimum oxygen content at each temperature. For sake of simplicity, the formula FeO will be used to represent the wustite phase in the remainder of this paper. Consider the reaction 2 FeO solid solution = 2 Femeta1 + Ozgas in which FeO dissolved in another oxide dissociates to metal and gas. The activity of FeO in the solid solution, relative to "pure FeO" in equilibrium with metallic iron as a standard state, is then expressed as Here Po, and po2 * are the partial pressures of oxygen of the gas phase in equilibrium with metallic iron and the oxide solid solution or "pure FeO", respectively. The equation holds only if the metal phase is essentially pure Fe. The oxide combinations used in the present investigation fulfill this requirement. Magnesia is so much more stable than FeO that for all practical purposes aFe = 1 in the metal phase present in all mixtures used in this investigation. I. EXPERIMENTAL METHOD 1. General Procedure. The experimental method used was analogous to that developed by Foster and Welch1 and used recently by Hahn and Muan.2 It consisted of four steps: a) Determination of the equilibrium between FeO and Fe. b) Determination of d-spacing change with composition in oxide solid solutions (FeO-WO). c) Equilibration of various members of the solid solution series with a metal phase and a gas phase of known oxygen partial pressure. d) Determination of compositions of solid solutions resulting from step (c) by means of data obtained in step (b). 2. Starting Materials. General Aniline and Film Corp. carbonyl iron powder, type HP, was used as the source of metallic iron. A representative analysis was as follows: Fe, 99.6 pct; C, 0.01 to 0.04 pct; 0, 0.1 to 0.3 pct; N, 0.00 to 0.05 pct. Other elements were present as traces only. Wiistite was prepared from "Baker Analyzed" Reagent grade Fe2O3 of reported analysis as follows: Assay (Fe2O3), 98.8 pct; insoluble in HC1, 0.02 pct; not precipitated by NH,OH, 0.02 pct; Zn, 0.003 pct. Production of wüstite was achieved by a two-step

Jan 1, 1962

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl' who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By Paul M. Tyler

YEAR after year, the kaolin industry of the United States has been setting new production records and making better products. High-grade paper, pottery, and rubber clays are produced in this country mostly in the South. Georgia alone contributes over 70 pct and South Carolina almost 20 pct of the total domestic output. Residual kaolin is mined in North Carolina, highly plastic but naturally sandy Tertiary (Eocene) potting clays are worked in north central Florida, and good white clays are produced in several other states, but the main sources of kaolin or china clay have been numerous deposits in the Tuscaloosa (Upper Cretaceous) formation. This formation of generally sandy sediments is called the Middendorf member in older geologic reports and corresponds in age with some of the New Jersey clays. As shown in fig. 1, it crops out almost continuously in a generally southwesterly direction across South Carolina and Georgia and into Alabama. Clay is mined from this formation in all three states but the principal producing centers lie within about 10 miles of a straight line drawn between Aiken, S. C., and a point about 10 miles south of Macon, Ga. The white kaolins of the South were recognized and used prior to the Civil War but suitable treatment processes were not introduced until World War I when imports, chiefly from England, were curtailed. Although imports of high-grade clays were resumed after 1918, the domestic industry managed to treble its prewar production record during the early 1920's and has continued to grow. Whereas the 1909 to 1913 average total production in the United States was only 132,104 short tons valued at $705,352 f.O.b. mines, the output in 1948 was 1,-568,848 tons worth $19,756,738. Paradoxically, it seems in retrospect that the early failure of the American industry to meet foreign competition was due to the superior quality of our sedimentary clays in their natural state. Kaolin, of course, is the principal decomposition product of feldspars which originate in acidic igneous rocks such as granite, aplite, alaskite, granodiorite, quartz porphyry, etc. English china clays occur in residual deposits and before they can be marketed they have to be treated to remove accompanying quartz, mica, and other impurities. Notwithstanding the relatively crude methods employed, the final product is a beneficiated clay which is subject to a certain amount of technical control as to quality and uniformity. Although the naturally concentrated deposits in Georgia and South Carolina contain some of the finest crude white kaolin in the world, even it can be made better by suitable treatment. In recent years well over half of the high-grade china clay produced in the United States has been used in making paper. Some qualities of paper clays are still produced by the dry process, or air flotation, but the paper industry's specifications have grown so exacting that wet processing was adopted and more refined methods had to be perfected. Notwithstanding notable advances in clay-preparation technology during the past decade, or possibly because these advances have implemented and encouraged technologic changes in consuming industries, demand has grown for products of higher uniform quality than can be obtained from even the best natural deposits without rigidly controlled fractionation. Largely as a result of the wide adoption of machine coating for paper, the clay industry has been obliged not merely to eliminate virtually all mineral impurities but also to segregate the clay substance itself into narrow particle-size ranges. By extraordinary coordination of sales effort and production technology, several Georgia companies manage to market a wide variety of specialized joint products but the commercial success of many producers depends upon their mining only the best parts of their deposits and then skimming the cream of this almost pure clay in order to obtain a maximum yield of kaolinite finer than about 2 microns in maximum particle size and possessing low viscosity as well as the more familiar attributes of suitable color and brightness, or reflectance. To the casual visitor from another mineral industry, the kaolin mines and plants may appear to be

Jan 1, 1951

By Jean-Jacques Prompsy, J. S. Rinehart

Some time ago a study was initiated at the Colorado School of Mines in an effort to arrive at a better understanding of the stress fields developed within drill bits under dynamic loading and the influence that these stress fields could have on the failure of the bits. Particular emphasis has been given to the influence that bit shape has on the establishment of highly localized, potentially destructive stress inhomogeneities within the bit. The study has been divided into three phases involving three velocity regimes: impacts at very low velocities, 0 to 20 ft/sec, a velocity range in which dynamic effects are just beginning to be found; impacts at velocities ranging from 20 to several hundred ft/sec, a range commonly encountered in practical drilling operations; and impulsive loading through the detonation of explosives, a region in which the dynamic effects are greatly exaggerated and made more identifiable. The ultimate objective is to provide basic data which will enable the mitigation through judicious design of the frequency and severity of these transient concentrations of intense stress, thereby prolonging and increasing drill efficiency. This paper presents results of the third phase of this study — the development of a better understanding of the dynamics and mechanics of failures caused by transient stress-wave interactions. The impulsive loading or transient waves in these experiments were generated by detonating small explosive charges placed on the ends of Plexiglas cylindrical rods terminating in truncated cones. Under such intense loading, dynamic effects are greatly exaggerated and, hence, made more identifiable. The explosion generates a high-intensity transient stress disturbance which moves through the rod, reflects from surfaces which lie in its path, and establishes momentarily narrow regions of high concentrations of stress where failure of fracture may occur. The peregrinations of these waves, their interactions and their effects have already been described in the literature (see, for example, Refs. 1 and 2). The locations and extent of the regions quite apparently are strongly dependent on specimen shape, making it possible through judicious shaping of specimens to relocate the highly stressed regions, minimize their extent, or eliminate them entirely. These experiments were designed, first, to identify more clearly the vulnerable regions in geometries relevant to drill-bit design and, then, to modify these regions in a predictable way by changing specimen shape. Through this latter process, it is anticipated that better bit design might evolve. The specimens used in the experiments were cylindrical rods, 1 1/2 and 1 1/8 in. in diameter, ended by a truncated cone, with the cone angles ranging from 45° to 130°. Upper cone face diameters were 1/2, 3/4, or 1 in. A small plastic-covered electric blasting cap detonated on the axis of the specimen produced the spherical shock wave. The detonators used were Olin Mathieson No. 6, which induced into the rod a transient saw-toothed stress disturbance of about 3-microseconds duration, corresponding to a wave length of 0.3 in. in the Plexiglas. Five distinct systems of fracture were observed: (1) along the axis of the rod, a lower system of fractures, the cracks focusing around one point for specimens having cone angles of 80° and 90° and, as the cone angle was increased, spreading downward; (2) just above these fractures, an upper system of fractures composed of horizontal cracks observable in some specimens but not of any appreciable extent; (3) a third system of axial cracks still above the latter, observable in the small cone-angle specimens; (4) in the upper part of the specimen, a system of radial fractures extending from the blasting point; and (5) circular spalling due to reflection of the wave on the boundary of the cylinder. Only the first three systems, the axial fractures, are examined here. LOWER TENSILE FRACTURE SYSTEM The first, lower system of tensile fractures, shown in the photograph of Fig. 1, was observed in almost all of the specimens. It was due to the reflected tensile wave coming in from the boundary of the cylinder as shown in Fig. 2. The reflected wave was cylindrically convergent and focused

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By R. G. Treuting

Germanium single crystals strained in tension at 600°C slip on the {Ill} plane and, macroscopically at least, in the <110> direction. Deformation is in homogeneous: various localized rotations are observed, as is a banding consistent with secondary slip banding. The structure after deformation is polygonized with a domain size of about 2x1O-3 cm. In relaxation tests, an incubation period prior to flow is observed, of duration inversely related to temperature and applied stress. Under continuous loading, there is a sharp first yield point. A critical resolved shear stress therefore must be cited with respect both to temperature and to rate of loading. At 600°C, when loading proceeds at 2900 psi per min, it is 1310 psi. The yield point phenomenon is suggestive of Cottrell&apos;s solute atom atmosphere theory and five points of qualitative agreement with this theory are found. PLASTICITY of germanium at elevated temperatures has been reported by Gallagher,&apos; who ascribed it to slip on {Ill) planes and described some associated effects. Preliminary experiments with single crystals of silicon and germanium loaded as simple beams confirmed {ill) as the slip plane of both materials.V his was demonstrated by the standard technique employing traces on two surfaces of known angle on a deformed crystal of known orientation.3 These experiments did not fix the slip direction, since more than one glide system operated. Uniaxial tensile straining is preferred for this purpose in order to restrict slip to one predominant system and to provide an unequivocal determination of the orientation change with respect to the stress axis. Experimental Method Specimens were diamond-sawed from germanium crystals containing about 5x10-5 wt pct Sb prepared by the zone-leveling process described by Pfann and Olsen;4 these specimens measured about 81/2 in. long, 0.20 in. wide, and were of various thicknesses from 0.035 to 0.060 in. Prior to testing, a specimen was coated over 1 in. or more of length at each end with Apiezon wax, chemically polished (in a solution of 15 ml HF, 25 ml HNO,, 15 ml CH3COOH, and 3 to 4 drops Br2), and dewaxed in warm xylene. A brief re-etching after scribing through a complete wax coating with vernier dividers provided gage marks at 0.200 in. intervals on the polished surface. A specimen with grips soft soldered to the ends was passed through the furnace tube and the grips pinned to the tensile machine in series with a stress gage. The Schopper testing machine is best described by reference to the illustration on p. 107 of Schmid and Boas5 and is operated with the pendulum arm locked, fixing the upper head. Load is applied through the screw-driven lower head, manually or by reduced speed motor. The furnace is 21/2 in. long surrounding a 4x7/16 in. ID quartz tube and was positioned about the specimen to permit free motion. The inert or reducing atmosphere required was sufficiently provided by a flow of helium introduced at the center of the furnace tube, with the tube ends loosely plugged with asbestos paper. Surface corrosion was slight. The stress gage employs a Be-Cu strip with SR-4 units incorporated in a simple bridge network with provision for balancing and calibrating. The bridge output on loading is fed through a Leeds and North-rup dc amplifier to a Speedomax 10 mv recorder, and calibration is obtained by dead loading. Experiments of two types have been conducted. Most have been in relaxation at constant elongation. One stress-strain curve has been taken with the machine continuously driven. Following extension of a specimen, Laue X-ray photographs were taken to obtain the orientation change between deformed and undeformed regions, recorded on a single film by translating the specimen in a plane normal to the beam between exposures. Sequences of such multiple exposures were made on some specimens to include the entire orientation range on one film. Slip Direction To obtain a maximum orientation change with a single slip system, crystals of very closely <110> axial orientation were used. The classic determination of slip direction rests on establishing that direc-

Jan 1, 1956

By Walter A. Backofen, Donald H. Avery

Intense primary and cross-slip traces were observed in easy glide on Cu: 6 pct-A1 single crystals deformed in tension. A mechanism of cooperative source operation is developed which recognizes that both the applied stress and that resolved from dislocation arrays contribute to the stress on a source. By considering the stress from arrays, the activation of secondary systems in easy glide and the difference in appearance of slip markings on pure and solid-solution crystals are explained. Furthermore the cross-slip system is predicted to be second favored during easy glide for a large range of orientations. FROM many studies of easy glide in fcc metal crystals, a pattern of observations has developed which still requires full explanation. In pure copper, aluminum, and silver, the easy-glide, slip traces are fine and uniform with steps 50 to 100A on the primary* system.1-4 Yet it has not been at all clear why slip in the pure materials should occur in this way. On the contrary, one might expect, with simple slip and a low hardening rate, that the weakest sources on the primary system would operate extensively to produce strong slip traces. In a brass, however, intense slip steps up to 0.5 are found on both primary and cross-slip system4,6-9 seeger10 has pointed out that in a material of low stacking-fault energy such as a brass, extensive easy-glide cross-slip could not be thermally activated, but rather must originate on the cross-slip plane. In further explanation, the wilsdorfs4 and seeger10 noted that only the cross-slip system would not harden differently than the primary, whatever the latent hardening tendencies of other systems; therefore, in brass, which exhibits high latent hardening, the cross-slip is the only secondary system which could be expected to operate extensively, once it became active. The explanation of how the cross-slip system, on which the applied stress is low, becomes activated has been related, in a nonspecific way, to pileups by Hirsch11 and Honeycombe.l2 In the work to be described, deformation traces on solid-solution Cu: 6 pct A1 single crvstals were studied with conventional light microscopy and a mechanism proposed to explain both the observed activation of secondary systems in easy glide and the difference in appearance of slip markings on pure and solid-solution crystals. EXPERIMENTAL In preparing the Cu-A1 single crystals, rectangular bars approximately 0.4 in. by 0.4 in. by 6 in. were first machined from ingots made by vacuum melting copper of 99.999 pct and aluminum of 99.99 pct purity. They were then packed in powdered graphite and the crystals grown in a modified Bridgman apparatus at a rate of 5 mm per hr under an atmosphere of purified nitrogen. Crystal perfection as indicated by Laue back-reflection spots was good except for the last inch to freeze, which was discarded. Orientations so determined are shown in Fig. 1. Tensile specimens with a reduced gage section were obtained by masking the ends with electrical tape and chemically polishing in a solution of 20 pct HNO3, 24 pct HAc, 52 pct H3PO4, 2 pct Hcl, and 2 pct H20 at room temperature.13 Finally, the specimens were electropolished in a 30 pct ortho-phosphoric acid bath at 12 v. Tensile deformation was performed in an Instron testing machine at a strain rate of approximately 1 pct per min. During easy glide, extensive cross-slip was observed with all crystals, in spite of the low Schmid factor on this system, and in no case was any other secondary trace encountered. A certain sequence of slip-line development was associated with the extension. At yielding, intense primary traces passing completely through the crystal developed at some point on the gage section, generally near the grips; weak cross-slip traces also appeared, extending from the primary traces into the adjacent undeformed crystal, Fig. 2. Further extension led to primary traces adjacent to the first-formed and connecting with those of the cross-

Jan 1, 1963

By R. E. Reed-Hill, W. H. Hartt

The second order, {1011}-{1012} twin bands observed in critically deformed magnesium are often accompanied by an unusual form of kinking. These kinks, which lie adjacent to and run more or less parallel to the twin band habit, allow plastic deformation that occurs inside the twins to be accommodated into the matrix. The bend planes of these kinks cannot be explained using slip dislocations with Burgers vectors lying in the basal plane. A mechanism involving a single set of {1012)(1011) dislocations is proposed to account for the kink band habit, in good agreement with the experimental observations. It has been shown that second order, {101l)-{1012} twinning is an important phenomenon for magnesium deformed in the ambient temperature range. A detailed study of these twins has recently led to a better understanding of their irrational habit plane1 and their relation to fracture in magnesium.&apos; This paper is concerned with a third aspect of these twins; this being the kink bands, originally referred to as shear accommodation kinks,3&apos;4 that are often induced in the adjacent matrix. A twin band and its shear accommodation kink usually appear as a single macroscopic deformation, as seen in Fig. 1. The complex nature of these deformed regions is easily revealed, however, with the aid of a suitable microscope. It has been proposed374 that the primary function of these kinks is to accommodate the nonhomogeneous deformation that normally occurs in the second order twins. The twins tend to form as small discrete lamellae lined up approximately one in front of the other.&apos;&apos;&apos; Very large plastic deformations varying in magnitude from one twin to the next, may occur inside these lamellae. The kinks serve both to pass this strain into the matrix and to accommodate strain variations between twins. Deformation within the kinks, subsequent to their formation, has also been observed;3,4 and it is thought that this contributes to the strain accommodation process. The bend planes of the kinks have a habit near that of the twin band itself, which lies about 56 deg from the matrix basal plane. This orientation does not bisect the angle formed between the basal plane to either side of the bend plane and therefore differs markedly from the kink structure usually observed in hcp metals.&apos;-&apos; The present paper reports the results of a study of shear accommodation kinks and proposes a possible solution to the problem of the orientation of the bend plane. EXPERIMENTAL PROCEDURE Rectangular cross-section tensile specimens with axes parallel to (1010) and faces to (1210) and (0001) were cut and acid machined from a high-purity magnesium single crystal. After straining on an Instron machine the specimens were examined by both optical and replica electron microscopy. The basic procedures have been previously reported."&apos; EXPERIMENTAL RESULTS AND DISCUSSION Structure of Shear Accommodation Kinks. A typical, large (101l)-{1012) twin band with its associated shear accommodation kink is shown running diagonally from upper left to lower right in Fig. 1. In this optical micrograph the twin band, consisting of a row of small, highly deformed twin lamellae, is visible as a narrow dark band along the left hand edge of the structure in question. The kink lies to the right of the twins, is approximately three times as wide, and is lighter in contrast. The horizontal slip lines visible on the general specimen surface correspond to matrix basal slip and are parallel to the tensile axis. Note that on the right-hand side of the band these slip lines can be followed from the matrix into the kink. At the kink band boundary the slip lines suffer a clockwise rotation of about 25 deg. Rotations of this magnitude are not uncommon. When a surface such as that in Fig. 1 is given an etch1 making it sensitive to polarized light, it has been observed that the slip traces in the kink are parallel to the basal plane trace in this region. This is in excellent agreement with the assumption that these regions are indeed kinks. Fig. 2 is an electron micrograph of this same twin band and kink. Note that a row of small supplimation pits has formed

Jan 1, 1969

By L. O. Bacon

IN the spring of 1952 Calumet and Hecla Inc. began a geophysical program near Shullsburg, Wis., in the Wisconsin-Illinois lead-zinc district, to assist the geological and drilling exploration programs. Sphalerite, the ore mineral in this area, occurs with a considerable amount of marcasite. In general the higher the percentage of sphalerite in the ore, the higher the percentage of marcasite; however, there may be mineralized zones high in marcasite but low in sphalerite. Orebodies in general are relatively narrow and elongated. Reconnaissance exploration of virgin areas consisted of drilling along lines at 500 to 1000-ft intervals. Whenever a mineralized zone was intersected additional drilling was done to determine whether or not the zone carried zinc percentages of ore grade and, if so, to delineate the body. Calumet and Hecla Inc. was interested particularly in a method that would show the direction and position in which to drill from the original discovery hole. This suggested a method of contacting the orebody, which occurs at depths ranging from 100 to 200 ft, with one electrode. After a number of procedures had been considered it was decided to use equipotential line methods. Instrumentation and Field Procedure: The power source used was a 400-cycle Signal Corps motor-generator having a rated output of 1200 w at 115 v. The detection unit consisted of test probes, a two-stage amplifier, and &apos;head phones for determining the equipotential line by audio null. Field procedure consisted of contacting the sulfide body in the hole by a specially built spring-loaded expanding electrode which would be lowered into the hole, in the closed. position, until it reached the mineralized zone. At that point the mechanism was released so that the arms would make contact with the walls of the hole in the same manner that a well-bore caliper does. This electrode was then connected to the generator, the other terminal of which was connected to the surface electrode. The surface electrode was either a point, a straight line, or a circular line electrode. The point surface electrode was placed at a considerable distance from the hole, that is, 2500 to 5000 ft, depending somewhat upon the depth to the sulfide zone and the distance from the hole containing the subsurface electrode to which exploration was considered. A higher voltage output from the power source would have been desirable, although no difficulty was encountered in determining null points to a distance of 500 ft. Straight line electrodes used were approximately 1000 ft in length at a distance of approximately 1000 ft from the hole containing the subsurface electrode. The circular line electrode used consisted of 4400 ft of bare No. 10 copper wire, which provided a circle of 700-ft radius. All line electrodes were fastened to the ground at 20-ft intervals with copper staples 4 in. long. Equipotential points were determined at 25 to 100-ft intervals. Location of the points was made by plane table and stadia. In open country with a three-man crew, the points were plotted as they were determined. With a two-man crew, pegs were placed at equal potential points and surveyed in after several equipotential lines were determined. Although interpretation of results given in this paper is qualitative, the paper as a whole would not be complete without a discussion of the theoretical distribution of potential due to a circular line electrode. The theoretical distribution would be required if a quantitative interpretation of the measured potential distribution were to be made. The theoretical potential distribution due to a circular line electrode can be obtained by means of Legendre polynomials. Using the method as developed by Weber,&apos; the potential for a circular line electrode in a semi-infinite, homogeneous, isotropic medium can be expressed, using the spherical coordinate system, as: V(r,n) = pi/2pR[S(r/R)nPn(cos?)Pn(cosa)]r<R [1] er V(r,a) =pI/2pr[S(r/R)Pn(cos?) Pn(cosa)]r>R [2] where: 0 is the angle at the origin, taken on the axis of the circular electrode between the axis and the line drawn to the circumference of the circular electrode. a is the angle between the axis and the radius, r.

Jan 1, 1957

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann&apos; and Pilling and Bed-worth. wott and Gurney&apos; have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.&apos; According to Wagner&apos;,&apos;&apos; silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,&apos; silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth&apos;s crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,&apos; resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

By E. J. Ripling

A NY mechanism proposed to explain hydrogen embrittlement in titanium and its alloys must, of course, be consistent with the experimental data that characterize this embrittlement. Unfortunately, however, the mechanical behavior of hydrogen-bearing titanium, at least a-ß titanium, has not been unequivocally defined. Lenning, Craighead, and Jaffee have clearly shown that hydrogen cmbrittles a-titanium by elevating its transition temperature, probably as the result of the formation of titanium hydrides. Therefore, in these alloys, hydrogen acts like at least one other interstitial contaminant, namely, nitrogen.&apos; On the other hand, ß-titanium has been shown by these same investigators to tolerate very large amounts of hydrogen without suffering severe mechanical damage.2 Mixing these two phases, however, to form the most important class of commercial alloys, the a-ß alloys, again results in severe hydrogen embrittlement, although the mechanism by which the embrittlement is produced is not of the same type as that which causes brittleness in a alloys. Ductility damage due to hydrogen increases as the strain rate is reduced in a-ß alloys, while embrittlement in a alloys increases as the strain rate is increased, since the latter is a transition temperature behavior. Steel, like the a-ß alloys, becomes more hydrogen sensitive at slow strain rates, suggesting that the mechanism producing the embrittlement in these two metals is similar. Brown and Baldwin&apos; described the hydrogen-produced ductility depression in steel as a function of testing temperature and strain rate by defining the slope of the two surfaces that produced the depression in a three dimensional chart, Fig. 1. One of these surfaces was given by the equations (de/de)4 > 0 (de/dT) < 0 [1] while the other was defined by the pair of equations Surfaces of the type given by Eq. 1 are suggested in two ways. One is an embrittlement mechanism wherein the diffusion rate of hydrogen is competitive with the rate at which the material is being deformed, as suggested by the planar pressure theory of Zapffe and his co-workers.&apos; The other is the diffusion controlled extension of Orowan&apos;s theory on delayed fracture in glass by Petch and Stables.&apos;&apos; Surfaces of the type given by Eq. 2 are also compatible with a mechanism of pressure build up in voids, according to de Kazinczy,&apos; since the solubility of hydrogen in the metal increases with testing temperature so that as the temperature is raised, the pressure in the voids is reduced. Kotfila and Erbin recently presented some data on the dependence of ductility on testing temperature and strain rate for the a-ß 3 pet Mn complex alloy at four different hydrogen levels.H Although data were presented for only three testing temperatures at three different strain rates, their results indicated that surfaces of the types defined in Eqs. 1 and 2 are produced in the alloy when the hydrogen level is sufficiently high—200 and 300 ppm—Fig. 2. Jaffee and his co-workers presented data on a number of different a-ß alloys which indicated the existence of surfaces of the type described by Eq. 2, but the ductility recovery at low temperatures as given by Eq. 1 was not found." In an attempt to aid in crystallizing this description of the ductility dependence of hydrogen-bearing a-ß alloys, tests were conducted by the author on a-ß titanium 140A with three different hydrogen contents. The tensile properties of two as-received rods and one vacuum annealed rod* were obtained over a range of testing temperatures and strain rates as shown in Figs. 3 and 4. Hydrogen analyses were made by the Battelle Memorial Institute on four pieces of the rod whose properties are shown as solid circles in Fig. 4. The hydrogen content of these pieces, taken at widely spaced intervals within the rod, were 280, 270, 289, and 270 ppm, indicating that the hydrogen content within a single as-received rod was quite uniform. One of the broken test pieces whose properties are shown in Fig. 3 as solid circles was also analyzed, and found to have a hydrogen content of 310 ppm. The analyses obtained on two of the vacuum annealed specimens were 92 and 170 ppm.

Jan 1, 1957

By R. Q. Shotts

This paper is a review of recoverable reserves of bituminous coal in the Southern Appalachian area, according to the latest published estimates. A few comparisons are made, some apparent trends are discussed, and some comments are made regarding the limitations of present estimates. The definition of Southern Appalachian area used in this report is somewhat arbitrary. It includes all the bituminous coal deposits of Alabama, Georgia, and Tennessee. All of West Virginia has been excluded. The East Kentucky and Virginia counties included were selected in connection with a literature study the writer made in 1959 of possible coal supply areas for the Tennessee Valley Authority. The selected counties were considered to be the only ones from which TVA might expect to obtain coal. The availability of coal from some of these counties is doubtful, but no other East Kentucky counties were considered more than remote possibilities. With these limitations, the Appalachian area covered is that from which producers of electric power and steel and commercial coal users, located in the Southeastern U. S., may expect to obtain their supplies of coal. Of course, it is recognized that coal from the eastern interior fields is also available to many of these same organizations. RANK AND QUALITY OF THE COALS Practically all the coals in the Southern Appalachian region are of high volatile A bituminous rank. An occasional sample indicates a slightly lower rank, but such samples may be oxidized or otherwise not representative. Some thin beds in Lookout Mountain and Sand Mountain in Alabama and Georgia, are low volatile bituminous coals, but they have not been mined extensively in modern times. There is a possibility that some of the deeper beds along the southeastern edge of the Warrior field of Alabama are near the Low-medium volatile bituminous dividing line. The Sewanee bed and some other minor ones of the Southern Tennessee field, some of the lower beds in Virginia, many beds in Sand and Lookout Mountains in Georgia and Alabama, one or more beds in the Coosa field, possibly some lower beds in the Cahaba field, and most of the beds along the southeastern edge of the Warrior field and the southern end of the Sequatchie anticline of Alabama, are of medium volatile bituminous rank. The quality of the Southern Appalachian coals is highly variable. Some of them, particularly such prevailingly thin ones as the Black Creek bed of Alabama and the Straight Creek bed of Kentucky, are unusually low in mineral matter— probably the lowest in the U. S. With the exception of certain beds and local areas, Alabama and East Kentucky coals probably have as low average ash and sulfur content as can be found in any sizeable coal area in the country. The sulfur content of Southern Appalachian coals is also variable, but few beds are consistently high in sulfur. In Alabama, sulfur generally increases from southeast to northwest across the Warrior field, but this trend is not quite as clear in the other states. A few beds in Northern Tennessee are prevailingly high in sulfur. All Southern Appalachian coals are potential coking coals if they can be prepared to meet chemical requirements. Only a comparatively small part of the medium volatile A bituminous coal, but most of the medium volatile bituminous coal mined is actually used for coking purposes. An estimate of reserves of coking coal under the requirements of present practice, could be compiled comparatively easily, but this probably has never been done. The reserve of coal that can be coked as an ingredient of a suitable blend is probably many times the size of the reserves of coal that will yield suitable blast furnace and foundary coke without blending. WHAT CONSTITUTES ECONOMICALLY RECOVERABLE COAL RESERVES? When one first realizes the vast extent of the coal-bearing rocks in the Southern Appalachian area, (see Fig. 1) the thought is likely to occur that the supply of coal is inexhaustible. This is particularly true on realizing that in some of the basins of thicker coal-

Jan 1, 1962

By P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.&apos;&apos;&apos; A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.&apos; In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.&apos;&apos;7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961