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By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By L. D. Jaffe, F. W. Cotter, E. Cordon

The hardenability of titanium-base alloys was studied by metallographic examination and hardness survey of Jominy specimens end-quenched from the B range. Analyses of the data led to the equation log J = -0.57 + 0.25 @ct Fe + pct Mn + pct Mo) + 0.19 @ct Cr) +0.16 @ct V) + 0.03 @ct Zr). Here J is the distance, in sixteenths of an inch, from the quenched end of a Jominy hardenability specimen in the position of peak hardness, for material quenched from the B range. This equation fitted the experimental data with a standard deviation of approximately 0.29. The effects of the elements Al, Sn, W, Cu, Ni, B, C, N, 0, and H, and of pain size, were not statistically significant or not practically significant. A check against hardenability measurements in the literature showed agreement within the stated standard deviation. The equation should be useful in estimating hardenability of new or modified titanium alloys. HARDENABILITY in a titanium-base alloy is the ability of the alloy to retain the B structure on quenching. An alloy with high hardenability will retain the /3 structure even when cooled relatively slowly from a temperature at which B or P plus a is stable. A low hardenability material will retain P only if quenched extremely rapidly from the range of p or 0-plus-a stability, or will not retain it at all, at room temperature. High hardenability is desirable in titanium alloys to be heat-treated to high-strength levels. Its value is by no means limited to large section sizes. With high hardenability, a material can be solution-treated and cooled at a variety of rates, either to give high strength directly or, more generally, to give a soft ductile condition from which high strength can be obtained by subsequent aging. With low hardenability, high strength can be obtained, if at all, only by very rapid quenching, and there will generally be little increase in hardness on subsequent aging; an alloy of this type is limited in its applicability. On the other hand, alloys of very low hardenability have some advantages in weldability; essentially, they are always in the annealed condition, after welding as well as before. For commercial alloys, hardenability data are usually available, in the form either of property data after cooling from the solution temperature at various rates, with or without subsequent aging, or of results of a standard hardenability test, such as that originally developed for steels by Jominy and Boegehold.' When modifications of an available alloy are considered, or preparation of new alloy compositions, it would be Very convenient to be able to estimate the hardenability of the new material without having to make and test it. A method of estimating hardenability of titanium alloys from their composition was suggested by one of the authors some time ago, on a preliminary basis, utilizing scattered data found in the literature.' It seemed worthwhile to carry out a systematic experimental study of the effect of composition upon hardenability. EXPERIMENTAL PROCEDURE Approximately fifty heats of various compositions, weighing 8 to 10 Ib apiece, were melted in a small inert-gas tungsten-arc furnace with water-cooled copper walls. The starting material was 110 Brine11 titanium sponge, with high-purity metals added for alloying. Each heat was bottom-poured under vacuum through a molybdenum burnout strip into a cold graphite mold, to form an ingot approximately 4-1/2 by 3-1/2 by 3 in.* From each ingot were cut *The material was melted and cast by Pitman-Dunn Laboratory, Frankford Arsenal, to whom the authors must express their thanks. two pieces 4-1/2 by 1-1/2 by 1-1/2 in. These were forged, at temperatures adjusted to the composition, into 1-1/4-in. rounds, from which standard 1-in.-diam hardenability specimens3 were machined. A number of small samples were also prepared from forged materials of each heat, annealed, quenched from various temperatures, and examined metallographically. The P-transus temperature was determined by observation of the degree of resolution of primary a in these pieces. samples for chemical analyses were also taken from the forgings. One hardenability specimen of each heat was solution-treated for 1 hr approximately 50°F above the measured transus temperature, and the other for 1 hr approximately 250°F above the transus. (An additional hour was allowed for the specimens to reach furnace temperature.) These are not necessarily the temperatures that would be selected for

Jan 1, 1964

By Norman Brown, Victor V. Damiano

ThE present paper proposes a mechanism of dislocation multiplication at internal inclusions or cavities and presents experimental evidence of such sources in zinc. Using an etching technique recently described by Damiano, Tint, and Herman1 to study the three-dimensional aspects of dislocations in bulk zinc crystals, an investigation was made of helically shaped and closed-loop etch patterns found to be associated with inclusions. Crystals containing 0.1 pet Cd and grown from the melt were deformed slightly by bending and then aged at room temperature to precipitate cadmium at the dislocations. The crystals were cleaved along the (0001) plane and then etched with Gilman's2 etch. Crystals were continuously viewed on the (0001) plane while the etching was in progress and numerous helical and closed-loops etch patterns were continuously recorded as shown in the sequences printed directly from the cine film in Fig. l(a) and (6). These etch patterns are not to be confused with the etch patterns previously reported by Damiano and Herman3 which revealed dissolution spirals on the (0001) plane of high-purity zinc crystals. In the present case, precipitates arranged in the form of closed loops or helicies are progressively uncovered by etching after suitable aging of cadmium doped zinc crystals. Viewed with dark-field illumination as shown in Fig. 2, portions of a helical figure and subboundaries were revealed simultaneously. Continuous viewing while the etching was in progress revealed in Fig. 1(b) that the short line segments observed on single photomicrographs were in fact continuous and described a helix which had its terminus at an inclusion. The observations suggested that a dislocation once nucleated at the interface between the inclusion and matrix may act in such a way as to produce ad-

Jan 1, 1964

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By Gary A. Kingston

This examination of Pacific Northwest (Idaho, Montana, Ore on, and Washington) ferrous scrap-industry opera ions, principally those in Oregon and Washington, points out factors influencing the supply and consumption of scrap materials, such as the complete dependence of steel ingot producers in these States on scrap as a metal raw material and the sizable quantity of scrap exported from Seattle and Portland to Japan. The pattern of the industry is presented as a movement of materials from their diverse sources to the consuming market. The geographic locations of the consuming industries in relation to the area generating scrap materials and the movement pattern of the supply from source to destination strongly influences the cost of the commodity. The best measure of the scrap supply available in an area is experience in terms of how much scrap was withdrawn at a given price. Scrap availability is not finite, because the return of materials as scrap is secular and influenced by constantly varying market conditions. Steel ingot producers use 75 percent of the approximate 500,000 tons of scrap consumed in Oregon and Washington; steel foundries take 15 percent of the total; and iron foundries, ferroalloy plants, and other miscellaneous consumers utilize the remainder. Also, from 1955 to 1960 an average of about 200,000 tons has been exported annually from Oregon and Washington. The foreign exports are supplemented by lesser .shipments to other steel producing States, principally in the western United States. From 1955 to 1960 the preferred and higher value heavy melting scrap grades accounted for about 60 percent of total withdrawals which varied between 600,000 and 950,000 tons annually. Total scrap withdrawals from Oregon and Washington are projected to 1.8 million tons by 1985, 60 percent (1.1 million tons) of which will be heavy melting grades. No. 1 heavy melting scrap is most attractive to scrap consumers at $35 per ton or less. Price-supply relationships compared with projected scrap requirements indicate future prices possibly over $35 per ton. High prices over a long period could motivate the Pacific Northwest scrap consumers to produce steel from iron ore. However, technologic changes taking place at integrated steel plants could reduce scrap withdrawals from the Pacific Northwest, which might keep the scrap price sufficiently attractive to obviate production of competitive iron products by the Pacific Northwest scrap consumers.

Jan 1, 1964

By D. E. Etter, J. E. Selle

HIGH-PURITY cerium metals, supplied as 99.9 pct pure, by various suppliers, vary widely in melting points and in the shapes of the differential thermal-analysis curves obtained as the samples are heated. A definite correlation is noted between the melting point, amount of premelting, and the number of inclusions present in the material. Briefly, the DTA apparatus, previously de-

Jan 1, 1964

By M. H. Pilkuhn, H. Rupprecht

The junction luminescence of GaAsxP1-x diodes containing up to 47 pct Gap was studied. Diodes were prepared by diffusing zinc into n-type material which was eithw boat- or vapor-gvown. Observations concerning the energy and the line shape of the spontaneous emission are presented and discussed; in particular the influence of inhomogeneous phosphorus distribution is considered. The role of reabsorption of the junction radiation is pointed out. With increasing current, the peak emission shifts to higher enwgy. This is alm true in cases where slow line narrowing occurs simultaneously. The length dependence of the threshold current density for lasing at 77 °K was examined for lasers made from the same material. It was found that longer lasers have lower threshold curvent densities, Estimates of the characteristic laser losses are given. Data concwning the range of Gap concentration in which stimulated emission was observed are presented. FORWARD-BIASED p-n junctions in mixed alloys of GaAsxPl-, emit light whose wave length depenfs on the composition of the alloy ranging from 8400A (x = 1) to 5350A (x = 0) at 77°K. Laser action in vapor-grown material was first reported by Holonyak and evacqua,' and in boat-grown material by Ainslie, Pilkuhn, and Rupprecht.' In both cases this was observed for low Gap concentration where GaAs,Pl-, is still a "direct" semiconductor with the lowest conductance-band minimum at k = 0 and a subsidiary minimum in the [loo] direction. As the Gap concentration is increased, the subsidiary [loo] minimum in the conduction band is lowered and finally becomes the lowest minimum for Gap concentrations above 50 pt,3 making the alloy an ''indirect" semiconductor. It is of interest to determine up to which Gap concentration stimulated emission can be observed. EXPERIMENTAL Boat-grown material was prepared by N. Ainslie of IBM by horizontal Bridgman technique. The material was n type and silicon-doped up to a concentration of 10'' cm-'. Vapor-grown material was made by E. Hull of IBM or received from Merck & Co. Diodes were fabricated in a similar manner as in the case of GaAs by zinc diffusion. Details about the diffusion can be found in a later paper.4 All diodes were of Fabry-Perot structure with two parallel sides cleaved and the other two sides sawed. Their width ranged from 50 to 150 p and their length from 50 to 700 p. RESULTS AND DISCUSSION Spectral Distributions. A typical display of the junction luminescence of a GaAsxPl-, diode is shown in Fig. 1. The liquid-nitrogen and room-temperature curves which were taken at a very low current (25 ma dc) show a relatively sharp high-energy emission which is band-edge radiation. They also show a broad low-energy emission which is due to transitions to deep impurity levels. This latter emission line may have different shapes and positions depending on the nature of the material. It can sometimes be quite near the band gap giving rise to "bumps" in the high-energy line. The results presented in this paper will be concerned only with the high-energy emission which becomes more intense relative to the low-energy emission when the current is increased and the temperature is lowered.

Jan 1, 1964

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By A. O. Drysdale

From a mining point of view the Portland Cement Industry falls logically into the Industrial Minerals Division. Portland Cement manufacture requires four principal materials, lime, silica, alumina and iron. The usual source of lime is limestone. Silica sources include clay, shale, quartz, sandstone and sand. Alumina is usually provided by selecting a silica source with a suitable alumina content such as clay and shale. "Cement Rock" is occasionally found in which all four ingredients are found in natural combination or sufficiently close that only minor adjustments are required. In the absence of iron oxides a white cement can be produced. All raw materials used in Canada contain some iron and in most plants further minor quantities of iron are added to promote fluxing, hence the typical grey colour of Portland cement. The modern period in cement manufacturing started in 1824 when Joseph Aspdin of England patented a process for the manufacture of a modified hydraulic cement which he called "Portland Cement". Hydraulic cements are cements that harden under water. Although natural cements, made by calcining and grinding natural argillaceous limestone were produced in Canada as early as the 1830's, Portland cement was not produced in Canada until 1890, about 18 years after it was first made in the United States.

Jan 1, 1964

The results of iron ore exploration in Western Australia between '1961 and 1964 are outlined, with particular.reference to the Hamersley Iron Province. Exploration during: these three years has increased the known resources of the-,Statle from 275 million tons to almost 9,000 million tons of high- grade hematite ore. In addition, reserves of lower-grade .pisolitic limonite ore are-estimated to amount to 6,000 million tons. The origin and characteristics of the different types of ore is discussed,

Jan 1, 1964

By Gill Montgomery

The problems of the domestic merchant fluorspar producers are more or less common with those of many other producers of metallic and non-metallic minerals. For more than ten years the American fluorspar producers have seen an ever lowering price in the market-place for the fluorspar product, while their labor and material costs-continue to mount steadily. This cost-price squeeze has forced out of business all but a few of the merchant producers, and only two captive producers continue to operate, and one of them has announced early curtailment. The prices of domestic fluorspar, of all grades, have declined because of the competition from cheaper foreign imports, principally from Mexico, Spain and Italy. Tariff protection on fluorspar, particularly on the highest or acid grade, has never been sufficient to cover the production cost differential between foreign and domestic fluorspars. Low ocean and barge freight rates have also contributed to the barring of the product of domestic mines from, the major consuming centers along the Gulf and East Coast. Because of the freight disadvantage, all but one or two fluorspar producers in the western states have had to suspend business. More than 80% of the domestic fluorspar is being produced in Illinois and Kentucky fluorspar districts which adjoin on both sides of the Ohio River.

Jan 1, 1964

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Robert B. Johnson

The refraction seismic method has been used as an indirect means of exploring for fluorspar in southern Illinois by the Illinois State Geological Survey. Use of the method has been restricted to those areas where mineralization is associated with faults, a restriction necessitated by the operating principles of the refraction method. The seismic data enable the interpreter to locate fault zones in the subsurface and, under ideal circumstances, to make estimates of dip direction and magnitude and vertical displacement provided the local stratigraphic units are known and are geophysically recognizable. In this instance, refraction seismic exploration has been successful in the surface mapping of well-developed faults, both simple and complex with which fluorspar may or may not be associated. However, less clear results have been obtained where faulting has been less severe and where there are numerous accompanying mineralized joints.

Jan 1, 1964

By C. O. Ensign

Results of the application of geo1ogic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphi-cally controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore. A routine program of grade control was started in the White Pine mine in August 1961. The program is based upon development and application of geologic knowledge to assist mine operating personnel to increase the grade of ore, primarily by accurate stratigraphic control and selection of areas for development on the basis of grade distribution trends. Geologists work closely with mine supervisors to offer the necessary geologic guidance. STRATIGRAPHIC POSITION OF COPPER The important rock series in the White Pine area is comprised of three formations of late Precambrian age. In descending order they are the Freda sandstone, Nonesuch shale, and Copper Harbor conglomerate. The Nonesuch shale is about 600 ft thick. Economic copper concentration occurs only in the lowermost 20 to 25 ft of the formation; however, within a restricted area along the southwest side of the mine the uppermost 1 to 7 ft of the Copper Harbor conglomerate (lower sandstone) contain sufficient quantities of copper to be included in the ore column. The ore consists primarily of chalcocite with subordinate native copper disseminated in shales, siltstones, and sandstones. MINE BOUNDARIES AND STRUCTURE The mine area is bounded on the west by the sub-outcrop of basal Nonesuch at bed rock surface and on the southwest by the White Pine fault (Fig. 1). The south and southeast limit of the orebody is reasonably well delineated by thinning or pinch-out of favorable host beds. Northern, northeastern, and eastern limits have not been established. The White Pine fault is actually a wide zone of shearing which strikes approximately N 40° W. It is downthrown on the southwest side and dips steeply to the northeast. Maximum vertical displacement is about 1500 ft.

Jan 1, 1964

The use of ammonium nitrate/fuel oil explosives is.now well established in most open cut mining operations. Its use. is extending to underground mining. This has been due in a large measure to improvements in the nature of the ammonium nitrate made available from various sources. The addition of surface active agents and water in controlled amounts to the fuel oil has been found to increase the sensitivity of the ANJFO mixture with consequent better explosive properties. It is considered that the surface active agent increases the bond between the ammonium nitrate and fuel oil giving a more, intimate physical and chemical mixing of the oxidising and reducing agent. This results in increased sensitivity and a faster rate of reaction. The increase in sensitivity has been accomplished without any diminution of safety. Tests which demonstrate the safety of this type of explosive are given in the appenuix.

Jan 1, 1964

By Horace Pops

Isothermal sections in the copper -rich region of the Cu-Si-Zn a1by system have been determined at 8473 760; 6003 and 482°C by means of microscopic examination with confirmatory X-ray diffraction work. The stability of the bee 0 phase decreases both with decreasing temperature and with increasing copper content. The silicon-n&apos;ch 0 phase decomposes upon quenching from high temperatures either by a martensitic or by a "massive" transformation, depending upon the solute content. A two-phase equilibrium is found to exist in the Cu-Si-Zn system between the hep < phase of the Cu-Si system and the bee ß phase of the Cu-Zn system. It is shown that the isothermal limits of the primary solid solution at 760; 6003 and 482°C are in part affected by the intermediate phases which follow them in the ternary system Possible electron-concentration and size effects upon phase boundaries are discussed. ALTHOUGH the mechanical and physical properties of silicon brasses have been measured in great detail, the factors which influence these properties are not well-understood, partly because the knowledge of the phase relationships in the Cu-Si-Zn system is limited. Gould and Ray1 studied the effects of silicon upon the hardness and structure of Cu-15 pet Zn and Cu-40 pet Zn alloys. They proposed an isothermal section at 800°C which was not based upon experimental data, since the binary phase diagrams had not been completely determined. Using Cu-Si-Zn alloys containing approximately 5 wt pet Si, vaders2 determined the boundary, at 750°C, between the copper-rich solid solution and an unidentified second phase. Masing and wallbaum3 examined a vertical section through the ternary diagram in the region between Cu-20 pet Zn and Cu-10 pet Si alloys, but they emphasized uncertainty about their data. Mima and Hasegawa4 studied the liquidus surface of Cu-Si-Zn alloys, phase transformations in high silicon-bearing (20 to 25 at. pet) alloys,5 and the phase relations in low silicon-bearing Cu-Si-Zn alloys.6 Their experiments were based upon thermal analyses and metallographic observations. The compositions of the phase boundaries were not determined with high precision, and the crystal structures of the phases were not reported. Because of uncertainties in the existing literature, it became of interest to determine more accurately the phase relations in copper-rich Cu-Si-Zn alloys. The crystal structures, stability, and phase boundaries of the primary solid solutions and several intermediate phases were determined, and the data are reported as partial isothermal sections.

Jan 1, 1964

The C.S.I.R.O. acid alumina process employs the essential steps of digestion, hydrolysis and calcination to produce pure alumina from ores too high in silica or too low in grade for the Bayer process. The two latter stages have been described in some detail previously but the digestion stage requires separate discussion since ores vary widely in composition and reactivity. Kaolinitic clays require roasting to 800&#176;C to render the alumina soluble in the 11 per cent sulphuric acid used in the process while some ferruginous laterites require roasting to reduce the reactivity of iron minerals.The iron content of pregnant solutions is kept at a low figure by digesting at temperatures where the solubilities of ferric oxide or basic ferric sulphates are small. A two-stage, counter-current digestion is necessary to extract a high percentage of alumina from the ores and to produce a basic pregnant liquor with an SO3 : AI 203 ratio of 1&apos;\1 suitable for high temperature hydrolysis. The second stage of digestion, called the modification stage, treats slightly acid liquors with excess of ore in the temperature range 1200-1400C.The first stage operates at 170&#176;-1900C to extract further alumina from modification residues, using recycled acid obtained from later steps of the process. Both temperature ranges are critical for economic operation and for proper control of the iron content of solutions. In batch experiments, 30 min is regarded as a suitable retention time for digestion and modification; ores which require much longer than this are less suitable for the process. Impurities such as silica, and titanium and vanadium oxides are discarded in the residue along with iron oxide, and do not contaminate the final product. Bivalent metallic sulphates such as MgSO4, can build up in the circuit to a very considerable degree without affecting product purity.Comparison with other processes shows that the C.S.I.R.O. process is superior for control of contamination by iron, which is the major problem in acid processes. The pure intermediate product (3Al203.4S03.9H20) is also more convenient for calcination to alumina than the hydrated aluminium sulphate usually recovered in other processes. Detailed cost comparisons must await pilot-plant evaluation of the C.S.LR.O process.

Jan 1, 1964

By F. R. Lee

[WHEN the Bureau of Mines was established in July 1910, one of the problems immediately attacked by the new organization was the development of standard, for the design and testing of electrical equipment that could be used without fear of initiating fires and explosions in underground coal mules. Research and investigation by Bureau personnel, supplemented by the published results of similar work by European mining authorities, led to the establishment of standards or "schedules." which guide manufacturers in the design of many types of electrically operated machines and devices used in. underground coal Mining. By issuing these standards, Bureau personnel establish the requirements to be met by such equipment before it tan be approved by the Bureau of Mines as permissible for use in gassy coal mines. Every 2 years the Bureau of Mines publishes a list of equipment that leas been accepted as approved or permissible during the preceding 2 calendar years. This is done to inform the mining industry of the availability of the latest equipment for safe use underground.]

Jan 1, 1964

By Chester O. Ensign

The White Pine Mine is situated in the southwestern portion of the Keweenaw Peninsula of Upper Michigan approximately 6 miles south of Lake Superior (Fig. 1). It is east of the Porcupine Mountains in Ontonagon County. The ore deposit is about 70 miles southwest of the famous native copper deposits of the "Copper Country" lying northeast of Houghton. Geological conditions are different at every mine and create a special set of problems in dilution control. This paper is largely intended to describe the techniques applied in mine dilution control (grade control) at White Pine, and present results of the program. For necessary background information major geologic characteristics of the deposit, particularly those that exert control over the distribution of ore, are briefly discussed. Mining methods are described in considerable detail since applied grade control techniques are adapted to these.

Jan 1, 1964