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By B. Ramaswami, Y. Nakada, R. Schaefer

EARLY investigations1 of the tensile properties of fcc single crystals did not reveal the easy glide region of crystals with axial orientations inside the standard stereographic triangle. With the production of high-purity metal, a region of easy glide became known1 Consequently, modern work of fcc single crystals ordinarily uses high-purity metal. In order to determine whether further purification of aluminum beyond 99.992 pct purity would result in significant alteration of the tensile properties of single-crystal specimens, metal was zone-refined and crystals grown from the purified material were compared to crystals grown from the original material. Some similar studies were made of gold and silver crystals. Aluminum. The material to be zone-refined was cast into bars 1/4 by 1/2 by 8 in. A zone, approximately 1-1/2 in. in length, was passed over each bar eighteen times at a rate of 6 in. per hr. Melting and stirring were carried out by an induction heater under a vacuum of approximately 10"5 mm Hg, the metal being held in a graphite container. he last 3 in. of each processed bar were then cut off and discarded. No quantitative determination of purity was made, but the effectiveness of the zone refining was tested by a method first suggested by Walton, Tiller, Rutter, and winegard3 depending on the relation between cell structure and impurity content. Rutter and Chalmers4 have shown that a cellular substructure is associated with the presence of impurities during solidificatibn, and have shown how solute rejection at the freezing interface can lead to such an association. Thus the observation of cells gives evidence of impurities being present. To look for cells, the last quarter of a zone-refined bar was cut off, remelted, and grown rapidly into a single crystal. It was then heavily electropolished and thermally etched.~ Cells were revealed by the presence of many parallel rows of etch pits. The same process was carried out with material from the first half of the bar, but no cells were detected. These observations give evidence that a significant amount of impurity material was moved to the "dirty" end of the zone-refined bars. Further indication of purification was obtained from recrystallization experiments. It was found that, after cold rolling to a 97 pct reduction in thickness, the material from the pure end of the bar re-crystallized at room temperature, but the material from the "dirty" end did not. Other investigators6 have previously reported that zone-refined aluminum recrystallized at room temperature. The purified material was cast into 1/4 by 1/4 in. bars, and seeded crystals were grown in a (100) orientation and in a single slip orientation where the Schmid factor is m =2. The crystals were then cut to the desired length, annealed for 24 hr at 610°C, furnace-cooled, and etched in Tucker's etch. The crystals were tested in a floor-model Instron machine, using a gage length of 4 in. and a strain rate of 1/2 pct per min. The resulting curves are shown in Fig. 1. It is seen that the differences between the curves for zone-refined and original-purity materials are small. These differences are within the scatter observed for crystals of the original purity. In particular, the zone refining does not significantly affect the onset of the different "stages" of the curves.

Jan 1, 1964

By A. D. Rich

The term "bleaching clay" or "bleaching earth," as used in the oil industries, refers to clays that in their natural state, or after chemical or physical activation, have the capacity for adsorbing coloring matter from oil. There are three common types of bleaching clays: fuller's earth, activated clays, and activated bauxite. Fuller's earth, or naturally active clay, is prepared from bentonites (see Chap. 5) that possess natural activity. It is not activated commercially; in fact, earths of this type ordinarily do not respond satisfactorily to acid activation. Fuller's earth is prepared in pulverized as well as granular form for use in the contacting and percolation processes, respectively. Acid-activated clays also are of bentonitic origin. The basic raw clay, however, is of a type that has a very low natural activity but is highly activable by treatment with mineral acid. Commercial acid-activated clays generally possess several times the decolorizing power (bleaching efficiency) of the best quality of fuller's earth. The former are prepared commercially only in the pulverized grade because of the difficulties in obtaining a satisfactory granular product, and hence are used only in the contact process. Activated bauxite is made by heat-treating bauxite ore, which in its natural state has very little natural activity. The commercial product is prepared in granular form for use in the percolation process on petroleum oils. For the most part, bleaching clay is used commercially in the decolorization of animal, vegetable and petroleum oils, fats and waxes. It is applied in two ways: (1) by the percolation method and (2) by the contacting method. Percolation refers to the passage of oil through a bed of granular clay whereas contacting refers to direct agitation of oil and pulverized clay followed by removal of the clay from the oil by filtration. In either case, the decolorizing effect is obtained by intimate contact between the liquid oil and the solid adsorbent. Petroleum oils are treated commercially by either the percolation or the contact process. Animal and vegetable oils are treated by the contact process only. Composition The raw clays from which both fuller's earth and acid-activated clays are prepared are composed of hydrous aluminum silicates containing varying quantities of magnesium, iron, calcium and other elements. These raw materials are usually nonswelling bentonites derived from volcanic ash or lava by weathering and hydrothermal chemical reactions. The bentonites have as their chief mineral constituent montmorillonite, which has the formula [(OH)4Si6A14O20•nH2O], according to Grim. (See Chap. 5, ref. 6, p. 91.) The underlying reasons are not fully known for the natural activity of the fuller's earth type of clay and its usual failure to further activate with mineral acid in contrast to the natural inactivity of the activatable type of clay. However, it may be said that the bentonites that are responsive to the acid-activation treatment generally have not undergone any drastic metamorphism. The chemical composition is not a reliable means of discrimination between a nonactive, a naturally active, and a nonactive but activable clay, therefore it is not possible to forecast the ultimate quality of a clay on the basis of the raw-clay analysis alone. Table 1 gives typical analyses of representative clays of the foregoing classifications.

Jan 1, 1960

By H. F. Mills

The Iron King mine is I2 miles east of Prescott Arizona, in low foothills of the Agua Fria mining district. It was operated in 1906 and 1907, using gravity methods of concentration, mostly on oxide ores. In 1923 and 1924 shipments of sulphide ores were made to the Humboldt smelter. It remained inactive and stripped unti1 1936, when it was unwatered and sampled to the 400-ft level, the bottom at that time. In 1937 the Iron King Mining Co. purchased the mine and shipped oxide ores. During 1938 a bulk flotation plant of I40 tons daily capacity was erected. The mill has been enlarged and operations have been continuous since the mill first started. In July 1942, the Shattuck Denn Mining Corporation purchased the physical assets from the Iron King Mining Co., and since that time it has operated as the Iron King Branch of the Shattuck Dcnn Mining Corporation. Economic metals recovered are gold, zinc, silver, lead, a little copper, and fluxing pyrite. The ore occurs as a series of northward-dipping shoots arranged in echelon pattern, the series extending over a length of 3500 ft. Strike lengths of shoots vary from 60 to 600 ft, and widths from 3 ft to as much as 14 ft. The ore occurs in a sheared zone in pre-Cambrian chloritic schist. This schist belt is about 6 miles wide, and the ore zone is about 4 miles from the pre-Cambrian granites to the west. No intrusive rocks have been found in the mine, nor is there evidence of any on surface that might indicate a genetic connection with the ore occurrence (Fig I). The schists strike N23°E and dip 75° to the northwest, which might indicate an overturned thrusting from the granites. In the upper levels, the echelon pattern in which the ore occurs was quite regular. no disturbance of the enclosing schist, or of any faulting that might contribute to the formation of the ore pattern was noted. There is a possibility that the ore zone may be on the axis of an isoclinal fold. Another interesting feature is the more or less typical zoning of minerals along the strike in each of the ore shoots (Fig 2). The north end of each shoot is enclosed by schist, while the south ends usually extend out at full width beyond the economic mining limits in a pyrite-quartz low-grade material. The plane of demarcation between ore and schist is very sharp, with little or no impregnation of sulphide in the schist, especially on the footwall side. The footwall schists are usually firm and strong, and vary from dioritic phases to fine-grained, lighter colored bands, almost silky in texture. The hanging wall for a width of 50 to 80 ft consists of alternating sheetings of chloritic and pyritic schists. The mine is now partly developed to the 920-ft level, with some diamond drilling from the 1150-ft station of No. 6 shaft. Economically there has been little change in nature or grade of ore from the top of the sulphides, about 200 ft below surface, to the bottom levels. There have been a few echelons in depth, just as there are in plan, and while a few shoots have had

Jan 1, 1949

By H. F. Mills

The Iron King mine is I2 miles east of Prescott Arizona, in low foothills of the Agua Fria mining district. It was operated in 1906 and 1907, using gravity methods of concentration, mostly on oxide ores. In 1923 and 1924 shipments of sulphide ores were made to the Humboldt smelter. It remained inactive and stripped unti1 1936, when it was unwatered and sampled to the 400-ft level, the bottom at that time. In 1937 the Iron King Mining Co. purchased the mine and shipped oxide ores. During 1938 a bulk flotation plant of I40 tons daily capacity was erected. The mill has been enlarged and operations have been continuous since the mill first started. In July 1942, the Shattuck Denn Mining Corporation purchased the physical assets from the Iron King Mining Co., and since that time it has operated as the Iron King Branch of the Shattuck Dcnn Mining Corporation. Economic metals recovered are gold, zinc, silver, lead, a little copper, and fluxing pyrite. The ore occurs as a series of northward-dipping shoots arranged in echelon pattern, the series extending over a length of 3500 ft. Strike lengths of shoots vary from 60 to 600 ft, and widths from 3 ft to as much as 14 ft. The ore occurs in a sheared zone in pre-Cambrian chloritic schist. This schist belt is about 6 miles wide, and the ore zone is about 4 miles from the pre-Cambrian granites to the west. No intrusive rocks have been found in the mine, nor is there evidence of any on surface that might indicate a genetic connection with the ore occurrence (Fig I). The schists strike N23°E and dip 75° to the northwest, which might indicate an overturned thrusting from the granites. In the upper levels, the echelon pattern in which the ore occurs was quite regular. no disturbance of the enclosing schist, or of any faulting that might contribute to the formation of the ore pattern was noted. There is a possibility that the ore zone may be on the axis of an isoclinal fold. Another interesting feature is the more or less typical zoning of minerals along the strike in each of the ore shoots (Fig 2). The north end of each shoot is enclosed by schist, while the south ends usually extend out at full width beyond the economic mining limits in a pyrite-quartz low-grade material. The plane of demarcation between ore and schist is very sharp, with little or no impregnation of sulphide in the schist, especially on the footwall side. The footwall schists are usually firm and strong, and vary from dioritic phases to fine-grained, lighter colored bands, almost silky in texture. The hanging wall for a width of 50 to 80 ft consists of alternating sheetings of chloritic and pyritic schists. The mine is now partly developed to the 920-ft level, with some diamond drilling from the 1150-ft station of No. 6 shaft. Economically there has been little change in nature or grade of ore from the top of the sulphides, about 200 ft below surface, to the bottom levels. There have been a few echelons in depth, just as there are in plan, and while a few shoots have had

Jan 1, 1949

By Fred D. Gustafson

With the postwar emergency for new housing and for new industrial buildings, much research has been done on lightweight aggregates for use in concrete and plaster. The trend toward lighter weight aggregates to relieve the dead load on the higher, steel framework buildings started toward the end of the last century. Progressively the requirements became more stringent, crushed bank slag, weighing 80 lb per cu ft as compared to 100 lb for crushed rock, was supplemented in some sections by foamed slags and expanded shales weighing from 40 to 60 lb per cu ft. In other sections cinders were used weighing from 40 to 50 lb, including sand. Sections favored with more recent vulcanism turned to pumice weighing from 30 to 60 lb, whereas other localities made use of diatomite, from 28 to 40 lb. Exfoliated vermiculite weighing from only 6 to 10 lb per cu ft came into use. As the search for lighter weights in aggregates continued so did the search for other desirable properties such as nailability, ease of cutting or channeling, and good insulation to both sound and heat. This search eventually led to a widespread interest in the expansion of perlite, or similar volcanic glasses, with the result that in 1946, the Office of the Housing Expediter' listed eleven firms reporting the operation of processing plants either on pilot or commercial scale producing aggregates weighing from 2 to 16 lb per cu ft. Geology Perlite is one of the large family of rocks originating from a granitic or acidic magma and generally has a "rhyolitic composition with a marked perlitic structure."² The name "perlite" is a derivation from "perlstein" originally given "to certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."3 The cause of the perlitic texture is somewhat controversial. Johannsen attributes the texture to strain set up in the glass by cooling and describes the finding of peculiar, glassy balls, called marekanite, more or less rounded and showing concave indentations, which may be left when perlite is broken. Frank Rutley, on the other hand, in 1881, while working on vitreous rocks from Montana, observed that there was incipient or partially started crystallization with segregation of water toward the un-crystallized portion in all specimens of perlite examined. Further he observed evidence of strain around focii of crystallization to which he ascribed the development of the spherical cracking which gives the rock its perlitic texture.4 Widespread over the western and southwestern United States where Tertiary vulcanism is exposed, perlite commonly is associated with andesitic, basaltic, and rhyolitic lavas with inter-bedded tuffs and ash of Eocene age although some deposits are associated with rocks assigned to the Pliocene age.5, 6 n nearly all cases the perlite overlies water laid tuff beds or agglomerates or breccias of explosive nature, an outstanding exception being the occurrence of perlite as the chilled selvage of andesite intrusions.7'8 Available chemical analyses of per-lites from the western and southwestern United States indicate that they are varieties of leucorhyolites rather than of normal rhyolites, leucorhyolites having less than 5 pct of dark minerals, normal rhyolites having more than 5 pct. This conforms with Johannsen's observation that leucorhyolites are the prevailing kind in North America.9 Tables 1 and 2 give

Jan 1, 1950

By R. DiBella, H. Biloni, G. F. Bolling

A study of the detailed relationship between solidification substructure and microsegregation in dilute tin alloys has been continued. New observations reveal that depressions form at the solid-liquid interface not only as an initial form of segregation but throughout the range of increasing constitutional supercooling. In order to show the importance of this node formation it proves convenient to make two simplifications. Although substructure changes continuously as constitutional- supercooling increases,&apos; the following discrete stages may be used for discussion: 1) the planar solid-liquid interface; 2) ordered nodes, or depressions at the interface;&apos; 3) two-dimensional or elongated cells;3 4) regular or hexagonal cells;4 5) distorted cells, or hexagonal cells with branches;4 6) dendrites. It is also convenient to ignore observations made near grain boundaries which interact with the cellular substructure.2-4 And, it should be clearly pointed out that all singular depressions at the solid-liquid interface will be called nodes. Heretofore, the term "node" has been used without clear justification to describe both the truly isolated depression and the junction of cell walls appearing in a later stage of segregation. This usage is continued because it seems proved by the observations. Standard systematic growth of tin crystals was undertaken over a broad range of constitutional supercooling using various added solutes. Except for one or two chance observations, this research failed to reveal any appreciable range of growth conditions over which a disordered array of isolated nodes exists. Even though &apos;some finite range of random instability must exist, it is now concluded that stage one passes very rapidly to stage two. Next, after confirming that stage two passes to stage three by the elongation of isolated nodes: a reexamina-tion of stages three, four, and five followed. Standard metallography showed that pockets of higher solute concentration (for ko < 1) became more numerous in cell walls the more severe the growth conditions. These high-concentration regions must arise from depressions; however, in stage three their segregation is not distinguishable from the segregation of the nodes which join cell walls together. It seems, therefore, that the presence of nodes is causal in the formation of new cell walls, and that the mechanism by which stage three passes to stage four is initiated by nodes. If a similar reasoning is followed, the separation of stage four from stage five appears to be just a convenience that has arisen from the decanted interface observations made in the past. The present observations again show that more severe growth conditions relate directly to an increase in the number of nodes in the hexagonal cell walls. These nodes apparently serve as the origin for lines of segregation extending within the body of a cell, and can thus be assumed to represent the earliest form of branching,* as shown here in Fig. 1. The examination of stage six involved decanted-interface structures as in Fig. 2, which are similar to those considered by Rutter and Chalmers,5 Plaskett and winegard,6 and Hellawell and Herbert,7 and where distinct protrusions are each surrounded by a depressed boundary. The corresponding microsegregation behind the interface, but not far enough behind to allow a smearing of the segregation because of diffusion,4 is shown in Fig. 3. Both the shape of the decanted interface and the segregation pattern behind it

Jan 1, 1968

By John E. Conley, John A. Ruppert

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors&apos; reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By John A. Ruppert, John E. Conley

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors&apos; reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By L. B. Schmitt, N. H. Polakowski

Square bars of cold-dvawn copper, mild steel and a 2024 aluminum alloy were forced through an adjulstable gap between two hardened steel rollers by pulling or pushing. The rollers were either free to rotate or were locked in position so that conditions comparable with drawing, rolling, ad containerless extrusion could be created at will. Push or pull forces as well as roll separatirg forces were measured. Forming efficiency and coefficients of friction were determined. For- slow-rate deformation the values ot µ wrere between 0.09 and 0.14. Possibilities for further investigation are indicated. THIS work was undertaken with the aim of a) determining the principal parameters of cold drawing under simplified conditions directly, without recourse to speculative assumptions and b) comparing drawing with rolling and extrusion from the viewpoint of forces involved and deformation efficiency. Data of type a) relating forces in axially-symmet-rical drawing to die geometry. drafting schedules, material properties and lubrication conditions are abundant. Their intrinsic value is. however. limited as long as the radial die forces are unknown. On the other hand. the difficulties associated with measurement of these forces are serious as witnessed by the extreme paucity of such information."" Comparative investigations of type b) were also remarkably few and they all employed ring-shaped dies through which round bars were either drawn or pushed.2-4 Only in one case were the applied and the die splitting forces measured simultaneously.2 In order to simplify the problem, deformation under approximately biaxial conditions was adopted in the present work;. This enables both the drawing (rolling, extruding) efforts and the separating forces to be measured with reasonable ease by conventional methods. Since drawing, extrusion, and rolling can be carried out under virtually identical conditions only in a roller die. an adjustable tool of this type was constructed. The circular die profile involved a difficulty with interpreting the drawing and extrusion data. This was obviated by arbitrarily defining the angle between a contact chord and the drawing plane as the -.equivalent" die semiangle. The simplification was considered permissible since the effect of die angle was not specifically investigated. An additional conlplication was caused by the square cross section of the processed bars. This shape was selected as a compromise between the desire to have as massive as possible specimens and the capacity of the roller die. The metal was only partially restrained from spreading laterally. the flow conditions being therefore intermediate between plane stress and plane strain. On the Huber-Mises yield criterion the constrained and uni-axial yield strengths differ by up to 16 pct but the actual error due to the ignorance of the constraint factor was presumably much smaller than the maximum. In spite of these reservations it was felt that the method employed and results obtained have some merit. With certain further refinements to be indicated later, this technique can yield data perhaps more useful for checking metal forming theories than other, mostly indirect, methods. EXPERIMENTAL Materials—The metals used together with their principal mechanical properties are listed in Table I.

Jan 1, 1961

By L. K. Jetter, C. J. McHargue

The use of axis charts for representing the texture of cold-rolled thorium sheet was compared with conventional pole figures. Four texture components were deduced from the axis charts and shown to be consistent with the pole figures. It was shown that consideration of the pole figures alone could lead to an apparent component which is the average of two actually present. It was also shown that the spread about the "ideal" textures and the amount of material associated with each could be readily obtained Fom the axis chart method. BECAUSE of the crystallographic nature of the deformation mechanisms in metals, plastic flow results in the alignment of certain crystallographic directions with the primary flow directions. In the study of the "preferred orientation" thus developed, one wishes to discern the distribution of the crystallographic directions with respect to some reference direction, usually a direction related to the fabrication procedure, such as the rolling direction. The pole-figure method, introduced by ever,&apos; involves the plotting of the distribution of the poles of some family of planes on a stereographic projection which places the reference direction(s) at the north pole and/or in the center. By noting the angles between the reference directions and concentrations of poles on several such pole figures, one can deduce the crystallographic directions which are aligned with the reference directions. If the preferred orientation is relatively simple and well-developed, one to three pole figures may be sufficient for obtaining the desired information; if there are several texture components, more pole figures may be needed. A significant improvement in the method of representing the textures in wires and rods resulted from the introduction of the "inverse pole figure" or axis-distribution chart by Harris.2 Such a chart gives directly the distribution of the reference axis relative to the standard stereographic projection. There has been widespread acceptance of this method for the representation of fiber textures, and methods have been proposed for converting observed diffraction intensities into axis densities.2-6 The suggestion by Mitchell and Rowland3 and Jetter, McHargue, and williams5 that sheet textures could be represented as distributions of rolling, normal, and transverse directions have been criticized on the basis that they offer no significant advantage over a combination of two ordinary pole figures and that it has not been proved that sheet textures can be treated as quasi fiber textures.6 If the purpose of a texture determination is to study some property which is related to the orientation of a particular crystallographic plane or direction, then conventional pole figures certainly are sufficient. For example, the distribution of the slip planes in face-centered cubic metals (the (111) pole figure) serves to indicate the variation in mechanical properties of sheet. On the other hand if the study is directed at an understanding of the factors influencing texture formation, it is desirable to know not only the preferred orientation but the kind and degree of spread from it and the relative amounts of material in each component, if there are more than one. Axis charts give this information as well as the orientation distributions. Consider the procedure for deducing a texture component from a pole figure for the (111) planes

Jan 1, 1961

By E. H. Griswold, C. E. Beecher

DURING 1931 the petroleum industry has faced the most hazardous periods of its existence, caused by large potentials, overproduction, and demoralized markets. Two state governors actually resorted to the use of the militia in an effort to restore a semi-stabilized condition within the industry, to prevent waste of the states&apos; natural resources, and to restore prices to a level that would yield the states a reasonable tax revenue. These conditions have made it necessary to put into effect most. stringent economies and have produced a spirit of cooperation between companies to an extent that never before existed. The necessity for unified action on such matters as proration and the advantages to be gained by unit operation are being realized by the oil industry as a whole. Fewer wells have been drilled and wildcat operations almost eliminated: development and operation costs have been greatly reduced and more attention is being paid to efficient recovery methods. The net work of oil pipe- lines has grown rapidly especially in the area of East Texas. The construction and operation of natural gas and gasoline pipelines into areas far distant from the source of supply has been one of the outstanding accomplishments. Refining efficiency has continued to increase and the public is being supplied with a better grade of gasoline at a lower price. The unreasonable tax which state politicians have succeeded in placing on gasoline has encouraged tax evasion and unfair competition by un- scrupulous dealers and has misled the public as to the true price of gasoline.

Jan 1, 1932

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman&apos; have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By AIME AIME

STRIP coal mining in the United States has-become noted for its massive equipment, especially its power shovels. Notable among the latest examples of this trend is the Bobolink mine of the Binkley Mining Co., at Seeleyville, Ind.,. eight miles from Terre Haute. This is only one of the Binkley company&apos;s operating properties; in all, the company owns or controls 26 mines, in fourteen seams. The Bobolink, however, is the largest strip mine in America and probably also in the world. It has an estimated life of fifteen years. The shovel used to strip the over¬burden is electrically operated, of Bucyrus-Erie make, and was. shipped to the property for assembling, a job

Jan 1, 1936

By Elton A. Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11. mile bus ride up Railroad Creek to Holden. A11 freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting. Ore is broken by long-hole blasting using the Noranda system which has been modified to meet local conditions. Until recently, blastholes have been drilled by diamond drills. Now a partial substitution of percussion drill holes, drilled with tungsten carbide insert bits, is being made. Geology The ore body occurs as a replacement deposit in a highly metamorphosed series of sedimentary rocks, mainly gneiss and schists, in a shear zone several hundred feet in width and of undetermined length. Commercial ore has been found in mineable widths of 25 to 100 ft for approximately 2500 ft along its strike. The commercial minerals are chalcopyrite, sphalerite, and gold. During the period of mineralization considerable silicifica-tion took place giving the ore an abrasive drilling characteristic. Following the period of mineralization, numerous dikes were introduced into the ore body. The earlier ones were of granite composition having a width of a few inches up to 80 ft. These were followed by much younger, fine grained basic dikes which usually do not exceed 2 ft in width. Development of Percussion Blasthole Drilling Equipment Test work with the 1½-in. tungsten carbide bit was carried on in development headings for several months early in 1947. The short life of the bits, because of gauge loss caused by the abrasive nature of the rock, prevented its adoption for this use. However fast drilling speed and ability to drill a long uniform hole suggested its use for drilling blastholes in competition with diamond drills as diamond costs were steadily increasing and exper-ienced drillers were difficult to obtain. The 1½-in. bit was the largest available at the time initial test work was started with sectional steel. The 1½-in. hole limited the diameter of the steel thread and coupling which could be used. Type F couplings were first used but because of the small thread section excessive breakage of the steel was experienced. Type H couplings were tried next. In order to use this coupling which is 15/8 in. in outside diameter, it was reduced to 1 3/8 in. giving 1/8 in. clearance between the coupling and the hole. Rod breakage at the thread was substantially reduced but some coupling breakage was experienced, however the overall performance was considered satisfactory (see Fig 1 for illustration of coupling and thread). Early test work with the 1½ in. bit indicated machines of piston diameters larger than 255 in. would cause inserts to loosen or break. It was found however that the additional weight of the sectional steel cushioned the blow enough to prevent bit failures when 3-in. Leyners were used. Rods used with the 1½-in. bits were 7/8 in. q. o. for sectional steel and 1 in. q. o. for all chuck pieces. In May 1948, 2-in. tungsten carbide bits became available and test work was immediately started. The 2-in. hole approximated the AX (1 15/16 in.) diamond drill hole which was being used exclusively for blastholes and permitted their substitution for diamond drill holes in a ring without alteration of pattern, burden, or explosives. The 2-in. bit also gave room in the hole for larger couplings and permitted the use of heavier rods and 3½-in. machines, increasing the

Jan 1, 1950

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen&apos; to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By N. F. Fiore, M. C. Mangalick

DISLOCATION damping in single crystals is orientation dependent.&apos; If dislocations are distributed uniformly over all the slip systems in a crystal, and if each dislocation contributes identically to the damping process, then a damping loss or decrement 6 arises. In fact, however, for a crystal of axial direction (hkl), dislocations on certain slip systems are oriented to make a larger contribution to the damping loss than are dislocations on other slip systems. Thus the measuring damping, 6 (hkl) is proportional to an orientation factor (hkl), which weights the ability of each slip system in the crystal to contribute to the total damping. If it is assumed that dislocations are distributed uniformly on all slip systems, then for a given orientation of an fcc crystal this factor is determined2,3 by the three nonzero elastic constants Cll, C12, and C44 and the density p. In this communication measured values of elastic constants for two Fe-18Cr-Ni alloys are reported, and the dislocation damping results on two different orientations of each alloy are analyzed for orientation dependence. Elastic constants were determined by measuring the ultrasonic velocities of one longitudinal and two shear waves in (110) direction of the fcc crystals.4 Variation of velocities with the change in orientation is very small for (110) orientation,3 and so this direction is ideal for orientation factor and comparative damping measurements. Experimental Procedures. The nominal compositions of the alloys studied are given in Table I. These alloys were vacuum-melted and vacuum-cast from high-purity materials at U.S. Steel Applied Research Laboratories. The single crystals were grown by the modified Bridgeman technique. The specimens were homogenized at 1350°C for 20 hr, cut to shape and size with a spark cutter, and then annealed at 1100°C for 20 hr prior to use. In the KHz frequency range, the Marx composite piezoelectric oscillator was used to obtain the damping. The ultrasonic pulse technique was used to measure the ultrasonic velocities and the attenuation in the MHz frequency range. M.c.mANGALICK,-- StudentMemberAIME,formerly Research Assistant, University of Notre Dame, is now with Casting Laboratory, Chase Brass and Copper Co., Cleveland, Ohio. N. F. FIORE, Associate Member AIME, is Assistant Professor, Department of Metallurgical Engineering and Materials Science. University of Notre Dame, Notre Dame, Ind. This communication is part of a Ph.D. thesis presented by M. C. MANGALICK to the Graduate School of the University of Notre Dame. Manuscript submitted May 20. 1968. IMD Elastic Constants. Table I gives the values of the ultrasonic velocities. Values of C11, C12, and C44 calculated from these velocities are also given in Table I, and it is evident that there is very little variation in C11, C12, and C44 with nickel content. This slight variation may be attributed to inaccuracies in velocity measurements and practical differences in the orientations of the specimens. For example, in B the time interval for vl was 2.4 ± 0.05 sec giving an error in v1 of 0.235 x or 0.005 in. per sec. The elastic constants obtained by pulse technique were tested by calculating E<110>, Young&apos;s modulus for the (110) direction, from the equation: This value was compared with the value computed from the resonance bar measurements in which where fr is the resonance frequency and I, is the length of the specimen. In all cases, the values calculated from the ultrasonic velocity measurements

Jan 1, 1969

By Kenneth A. Moon

Kenneth A. Moon (U.S. Army Materials Research Agency)—The authors are to be congratulated for a very interesting and valuable paper. Their discussion of the structural implications of the results shown in their Fig. 5, however, requires a small correction. The model of Speiser and Spretnak with 0 = 1 and z&apos; = 2 is perfectly reasonable for the Ti-O a phase, but Eq. [3] is valid only for solutions sufficiently dilute that the number of empty sites excluded by more than one filled site is negligible. The composition at which intrinsic saturation occurs therefore cannot be deduced from Eq. [3], but but must be decided by consideration of the structural details of the phase in question. In this case, intrinsic saturation is expected not at the composition Ti3O but at Ti2O, because Ti2O has the anti-Cd structurel4 for which each filled octahedral site has two nearby empty sites, one in the hexagonal plane immediately above it, and one in the similar plane below it. The other two models, with ?=1/3 and 1/2, imply a distinction between octahedral sites in pure titanium which is not easy to justify. The problem of extending Speiser&apos;s and Spretnak&apos;s treatment in a general way to more concentrated solutions will be the subject of a forthcoming publication by the writer. M. T. Hepworth and R. Schuhmann, Jr. (authors&apos; reply)—The authors wish to thank Dr. Moon for calling to their attention the paper by Holmberg which presents the results of X-ray studies of Ti-O solutions ranging from 0 to 33 at. pct 0 and quenched from various annealing temperatures between 400" and 1800°C. Within these ranges, Holmberg found three types of phases: 1) At high oxygen contents (above 25 at. pct) and low annealing temperatures, he found the anti-Cd(OH)2 structure referred to by Dr. Moon. In this structure each titanium atom is in contact with 3 oxygens and each oxygen is in contact with 6 titaniums, the "available" oxygen sites corresponding to every other layer of octahedral sites in the titanium matrix. The limiting composition is Ti2O. However, this anti-Cd(OH)2 structure was not observed for samples containing 25 at. pct 0 or less. 2) For the specimen containing 25 at. pct 0 annealed at 400°C an ordered Ti3O structure was observed. This structure is related to the anti-Cd(OH)2 structure but differs from it by providing only two oxygens adjacent to each titanium atom and thus is consistent with the model represented by Eq. [5] in our paper, with 6 = 1/3, z&apos; = 0. 3) For dilute solutions and for more concentrated solutions annealed at higher temperatures, the structure corresponds to that of the metal with random distribution of oxygens among all the octahedral sites. Thus, it is interesting to observe that the thermo-dynamic indications of ordering in the vicinity of Ti3O can now be supported qualitatively at least by Holmberg&apos;s X-ray evidence of the existence of an ordered phase of the composition Ti3O. That is, for solutions with oxygen contents close to that of Ti3O, both the thermodynamic data and the X-ray data are more consistent with models based on the ordered structure of Ti3O than they are with the model which Dr. Moon suggests corresponding to "intrinsic saturation" at Ti2O.

Jan 1, 1963

By M. J. Hordon, M. A. Wright

ReCENT work has indicated that the substantial decrease in the rate of fatigue crack propagation for aluminum observed below a critical vacuum level can be attributed to the depletion of oxygen or water vapor from the vicinity of the fatigue crack opening.&apos; At reduced gas pressures, generally below 10-2 Torr with fatigue strain amplitudes in the range *1 to 2 x 10-3 and cyclic loading rates of 25 to 50 cps, estimated rates of oxide or hydroxide monolayer adsorption on newly formed crack surfaces can fall behind the actual rate of crack extension. Changes in the critical pressure required for the transition in fatigue behavior with changes in temperature, strain amplitude, and cyclic frequency can be interpreted from variations in the adsorption and crack growth rates.&apos;" Although the adsorption model generally appears to explain the enhanced fatigue resistance of reactive metals in vacuum, the specific adsorbing gas species and nature of the adsorption mechanism are uncertain. In addition to the direct dissociation and adsorption of O2 on the metal surfaces,3 the dissociation of H20 and subsequent adsorption of H ions have been advanced for aluminum alloys.4 The present note describes some measurements of the fatigue behavior of 1100 aluminum in reduced partial pressures of specific gases including O2, H2O, and H2 in order to provide additional experimental data. Cantilever-type specimens of 1100-H14 aluminum were fatigued in cyclic reverse bending at constant strain amplitude using a multispecimen vacuum apparatus and procedure described previously.&apos; After initial vacuum evacuation to 1 x 10-7 Torr, the appropriate gas species was bled into the system through a calibrated leak valve. The input rate was adjusted to maintain the desired pressure level under continuous evacuation, thus minimizing possible changes in gas composition during testing. High-purity input gases including 99.9 pct O2, 99.999 pct H 2, and water vapor from triply distilled H 2 O were used to provide residual pressures. Trace amounts of contaminant species were limited by passing the Oz and H 2 input gases through liquid-nitrogen-cooled copper coils prior to entry to the test chamber. Care was taken to repeatedly flush the gas lines and valves before testing to minimize the effect of adsorbed contaminants. Residual gas pressures in the range 10-6 to 5 x x3 Torr were monitored by an NRC ionization gage corrected for each gas species. In the higher-pressure range, 5 x 1CT3 to 5 x 10&apos; Torr, an NRC alphatron gage was used. In operation, eight simultaneous fatigue tests were conducted at a constant strain amplitude of *1.2 x 10 at cyclic bending rates of 25 and 50 cps to give an average fatigue life of 6.5x 105 cycles-to-fracture at standard atmosphere and 3.3 x 106 cycles in 1 x 10"7 Torr vacuum. Representative results for the effect of residual O2, H2O, and H2 contents on the fatigue life are shown in Fig. 1 for tests performed at 50 cps. It is apparent that the presence of either O2 or H2O gas in the system at partial pressures greater than 10"3 Torr was noticeably detrimental to the fatigue life. In contrast, the enhanced fatigue resistance typical of high-vacuum environments was retained with pure H 2 through the pressure range up to 1 Torr. For partial pressures of H2 gas above 1 Torr, the fracture life noticeably decreased. The critical Hz

Jan 1, 1969

By D. W. Frommer, M. M. Fine

Mineral dressing research showed that iron concentrates of commercial quality could be produced from the Pea Ridge deposit near Sullivan, Mo. Magnetic separation and flotation, on a laboratory scale, yielded concentrates ranging from 60.0 to 71.4 pet Fe at recoveries of 89.9 to 97.6 pct. Early in 1957 St. Joseph Lead Co. announced discovery of three new centers of iron ore deposition in east central Missouri.&apos; The discovery resulted from exploratory drilling in the vicinity of a magnetic anomaly or high. A deep hole, drilled into the Pre-Cambrian porphyry to determine the cause of anomaly, penetrated a magnetite-rich deposit.&apos; The magnetic surveys that revealed the anomalies were begun by the Missouri Geological Survey in 1929 and were continued into the 1930&apos;s.3 At that time an area in Crawford County known as the Bourbon magnetic high was located. A second anomaly, similar in size and intensity, was discovered about six miles to the northeast in Franklin County in the vicinity of Sullivan. This area was not studied in detail until the early 1940&apos;s. To determine the cause of the anomalies, the USBM drilled four holes at the Bourbon site in 1943-1944.4 The most productive hole penetrated four mineralized zones having a total thickness of 127.5 ft. These zones contained magnetite in rhyo-lite porphyry at depths between 1600 and 2000 ft. Additional iron ore below 2000 ft was considered a possibility at the time. Some years later, the USGS, Missouri Geological Survey, St. Joseph Lead Co., and others cooperated in sponsoring an aeromagnetic survey of the Bourbon-Sullivan area which resulted in discovery of a third high, about eight miles distant at Pea Ridge. This deposit, with an estimated reserve of 50 to 100 million tons of iron ore, is considered the main find, although other orebodies in the same general area are of definite interest.&apos; When this discovery was announced, St. Joseph Lead also revealed plans to exploit the deposit jointly with Bethlehem Steel Co. A new corporation, Meramec Mining Co., was established, and 1962 was set as the target date for completing physical plant.2 Annual production goals of 2 million tons of beneficiated and pelletized iron ore were proposed. Preparation of the site for shaft sinking was begun in June 1957. Orebody and Character of Samples: Drilling to date has established the Pea Ridge orebody as a crescent-shaped pipe about 300 ft wide. Some drillholes were bottomed at 2800 ft in very good iron ore.6 he orebody is predominantly magnetite, although hematite and a mixture of hematite and magnetite occur in the upper areas and peripheral walls. Drillhole cores representing ore from different areas and depths of mineralization were grouped into composites for testing. These composites consisted of: 1) medium grade mixed hematite and magnetite, 2) high grade mixed hematite and magnetite, and 3) high grade magnetite. The medium grade ore came from three holes with depths of i350 to 1900 ft. The high grade mixed hematite and magnetite cores came from the 1790 to 2812-ft interval of one hole. Partial chemical analyses of the three samples, given in Table 1, reveal that all are excessively high in phosphorus and sulfur, and sample 1 is

Jan 1, 1960

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

NITROGEN is becoming recognized as one of the important elements in ferrous physical metallurgy. Several investigations indicate that nitrogen plays a significant part in such phenomena as strain aging and temper brittleness. Nitrogen is known to be a powerful austenite stabilizer and may be a useful alloying element in stainless steels. The hard-enability of steels has been found to be increased by nitrogen. The nitriding and carbonitriding pro- cesses are examples of successful industrial application of nitrogen in ferrous materials. For a complete understanding of the various roles played by nitrogen in ferrous metallurgy a knowledge of the phase relations in the binary iron-nitrogen system is essential. The literature contains a variety of iron-nitrogen phase diagrams. Those suggested by Fry, Sawyer,² Epstein and his coworkers,³,4 Lehrer,5 Eisenhut and Kaupp, and Hägg7,8 differ significantly from one another. Moreover, the most recent of these investigations dates back about twenty years. A re-determination of the entire diagram, therefore, appeared desirable. In addition to the published phase diagrams, investigations have been carried out on portions of the iron-nitrogen system. Bramley and Haywood determined the composition and temperature of the iron-iron nitride eutectoid. The maximum solubility of nitrogen in a iron was investigated by Portevin and Seferian10 and by Diikstra. 11 Several investigators have determined the crystal structure of the various iron-nitrogen phases. In fact, Eisenhut and Kaupp6 and Hägg7 based their entire phase diagrams on the results of such studies. Epstein&apos; and Emmett12 reported lattice-parameter measurements on the E (hexagonal close-packed) phase. Osawa and Iwaisumi13 also studied the change in lattice parameters of the a, ? and E phases with nitrogen content. Brill" and Hägg7 showed that the y&apos; phase has an ordered structure, and Hendricks and Kostingsl5 suggested a structural relation between the E and phases. In a recent investigation Jackl6 arefully studied the super-lattice reflections from the y&apos; and phases. Experimental Procedure A large variety of experimental methods has been used by previous investigators in studying the iron-nitrogen system. These methods include thermal analysis, microscopic examination, X ray diffraction, magnetic measurements, dilatometric analysis and anelastic experiments. Thermal analysis is of low accuracy in determining changes in the solid state. This accuracy is further decreased for iron-nitrogen alloys since composition changes will occur during heating or cooling unless extreme care is taken to use a proper atmosphere. Metallographic methods are of small value . because homogeneous iron-nitrogen alloys of sufficient size can be produced only with great difficulty. The dilatometric method is open to the same objections as thermal analysis in that changes in composition may occur during heating and cooling. Lattice parameter measurements by X ray diffraction can be used satisfactorily for determining phase boundaries if cooling is fast enough to prevent structural changes. In view of the limitations of the various other techniques two methods only were adopted in this investigation, (1) X ray diffraction measurements, and (2) a controlled nitrogenizing method. The second method is an innovation for investigating the iron-nitrogen system, and will be described at length. Materials: All iron-nitrogen alloys were prepared from carbonyl iron powder of the analysis shown in table I. The average particle size was about 20

Jan 1, 1951