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By W. C. Hagel

Previous inuestigators have repovted unusually low H* and Do values for self-dzf@szon in certazn bcc metals, e.g., chromium nnd y -uvanium. It has been postulated that this is nn experimental crl -tetion for the existpnce of a four -atom ring meclzanzsm, mid there could be. zmpovtant theoretrcal Implicatlons. By utilizing a precise sectioning technique with Cr51 as the tracer, self-dzffi-lsion measurements in large grains of 99.99-pct Cr were extended from 1200° fo 1600"C. A least- squares analysis of the data yields that D 0.280 exp (-73,20U/RT) cm2 sec-'. These AH* and Do unlues are not anomalous; there is little reason to believe that n vacancy mechanism is not opevatiue. Apparent differences at lower temperatures may result from preferential diffusion along short-circuititing paths and/or sample contamination. WITH continued technological effort, chromium and chromium-base alloys should ultimately become useful high-temperature structural materials. Accurate measurements of self-diffusion coefficients in the pure metal are necessary for a quantitative understanding of sintering, grain growth, creep, and other related rate processes. However, two conflicting determinations have been reported.* Using an Since careful diffusion studies normally yield Do values ranging from 0.1 to 10 cm2 sec-l, the Paxton-Gondolf results require independent experimental corroboration before an undue amount of speculation arises to explain the apparent anomaly. As discussed by Nowick6 and clearly shown by Hoffman and Turn-bull7 for self-diffusion in silver, a low AH* and Do can arise from preferential diffusion along grain boundaries or other short-circuiting paths. The most reliable data come from high-temperature measurements where volume effects predominate. Following a precise sectioning technique developed for determining silver diffusion in the intermetallic compound AgMg8 and cation diffusion in the corundum oxide Cr2O3,9 the purpose of this study was to measure true volume diffusion in high-purity, large-grain samples at higher temperatures than considered previously. Another point of interest is the frequent proposal10-12 that chromium undergoes an allotropic transformation between 1375" and 1800°C where the diffusion data might then show a discontinuity. I EXPERIMENTAL 1) Sample Preparation. The highest purity (99.997 pet) Cr currently available is produced by reduction of chromium tri-iodide. Three pounds of the resulting crystal bar were shipped in a sealed container with a complete chemical analysis from the vendor.* In conformity with the procedure used for

Jan 1, 1962

The use of pipeline-c to carry crude'oil and petroleum pro-ducts is a reliable and economic*Way to transport large quantities of oil. The length and size of these pipelines have continued to grow throughout the world as the demand for petroleum has in-creased and as the price of other transportation-methods has risen. At the present time pipelines 'can move a barrel of oil a distance of 100 miles at an average cost of ,80.06 U.S. dollars.The major elements in pipeline design are discussed. Methods of calculating pressure drop and horsepower requirements are pre-sented. These are variations of standard equations.in which the elements of each equation are expressed in terms common to the petroleum industry. Major equipment is discussed., particularlyas it relates to operation and economics.Cost data are presented to aid in preliminary economic ana-lysis. Curves illustrate the cost of oil transportation at flow rates between 10,000 and 500,000 barrels per day and permit the selection of pipe diameter-which will result in minimum operating costs.

Jan 1, 1962

By F. H. Gibson

In recent years physico-chemical techniques have been applied for rapid analysis of coal and coke ash as replacements for classical wet-chemical methods. Although the classical methods are accurate, they are time consuming because many chemical separations are necessary to complete an analysis, and they require skilled analysts for accurate work (12).4 For the past several years the Bureau of Mines has applied some of the newer physico-chemical techniques in its continued search for new and improved methods at analysis. The methods of analyzing coal and coke ash evolved from this work include spectrophotometric methods far SiO2, A120, , Fe203 , TiO2, and P2O5; chelatometric titration for CaO and MgO; and flame photometry for Na20 and K2O. The methods are rapid and direct, are suitable for analyzing a group of samples at the same time in production work, and dire results with almost the same accuracy as classical procedures. With the new methods, complete analyses in duplicate can be obtained at a rate of 2 to 3 times that of conventional methods.

Jan 1, 1962

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By J. Burlin Johnson

In small-scale blasting experiments conducted in the Bureau of Mines laboratory, small charges were used to produce craters in blocks of concrete mortar. The results are compared with larger scale experiments of other research workers, and the comparison demonstrates the similarity of the results obtained and indicates that small-scale blasting should be a useful tool for predicting large-scale blasting effects. INTRODUCTION The purpose at this investigation was to conduct blasting experiments in mortar in the laboratory and then, by comparing the results with those from larger scale field blasts in rock to determine to what extent, if any, the laboratory results resemble those in the field. The work described herein was the initial phase of a project aimed at evaluating small-scale blasting as a tool for use in improving blasting techniques. It is evident from the stand-point of control and cost that small-scale blasting would be valuable in the study of rock fragmentation by blasting in mines and quarries, if the extrapolation is valid.

Jan 1, 1962

Much of New Zealand is comparatively young geologically in the sense that it has only recently been uplifted. In many places young marine sediments are to be found at high altitudes, as evidenced by the existence in the North Island of Pliocene shell limestones which form prominent escarpments at altitudes of about 3000 ft. inthe central part of the Island, and remnants of the same formation found on the summits of the northern Ruahin.e Range at altitudes greater than 4000 ft.

Jan 1, 1962

By C. Richard Honeycutt, Frederick C. Langenberg, Guenter Pestel

Otto Schaaber (Institut für Harterei-Technik, Bremen-Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By K. E. Tame

Pollution from radioactive nuclides, principally Ra226, in liquid waste from uranium mills can be minimized by reusing the waste solution within the mill. Such reuse of waste solution in the Vitro Chemical Co.-type process was investigated in the laboratory. Vitro employs an acid leaching process for dissolution of the uranium, countercurrent decantation for liquid-solid separation and washing, and amine solvent extraction for recovery of the uranium from solution. The simulated reuse of barren raffinate in the mill circuit was carried through two separate laboratory campaigns of 29 and 31 cycles. Conventional chloride stripping of the amine was employed in the first campaign, whereas nitrate stripping was used in the second campaign. Dissolution of uranium from the are in the acid leaching circuit averaged 96 percent. Washing efficiencies of 98 to 99 percent were attained by using 4 volume tons of combined raffinate and makeup water per ton of ore. Uranium recovery from the pregnant solution using a 5-percent solution of amine LA-1 in kerosine ranged from 99.3 to 99.9 percent.

Jan 1, 1962

Naturally occurring organic plastics have been in use for over 2,000 years. Plastics based on chemically modified organic polymers date back only about 100 years, and those based on synthetic polymers about 50 years. The development of ,these two latter groups up to the present day is outlined, and the basic techniques currently available for polymer-building and modi-fication (blending, copolymerisation, quantitative and qualitative struc-tural control, and'si de-group reactions)-are reviewed.

Jan 1, 1962

By Ling Yang, John Henderson

Self-diffusion coefficients of copper in molten copper have been measured by the capillary reservoir method in the temperature range 1140o to 1260°C. The results can be represented by the equation D = [(1.46 * 0.01) x 10-3) exp [(-9710 * 710)/RT] cm2/sec. The energy of activation agrees within the limit of experimental uncertainty with that for viscous flow. The relationship between the diffusivity and coefficient of viscosity is best described by the equation D = kT/4pnr cm2/sec. MEASUREMENT was made of the self-diffusion coefficient of copper in molten copper in the temperature range 1413º to 1533ºK, using the capillary reservoir technique and CU64 as the radioactive tracer.The procedures for filling the capillaries, making the diffusion run and evaluating Dcu from the counting results were the same as described previously.1,2 All experimental operations involving the melt were carried out in a purified argon atmosphere. A graphite crucible, enclosed in a McDanel tube, was used as a container for the melt because of its satisfactory nature as a refractory material and the low solubility of carbon in copper. Graphite was also used for the capillary material. A McDanel thermocouple sheath, to which graphite radiation shields were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube, the capillaries could be lowered into or raised out of the melt. A Globar furnace with a constant temperature zone (± 2°C) of 2 in. was used to heat the assembly. The temperature of the furnace was the equilibrium value corresponding to a given setting of the transformer. Temperature was measured with a Pt-10 pct Rh/Pt thermocouple and varied during a run

Jan 1, 1962

By R. J. Weege, A. W. Schillinger

Conventional underground mapping methods and diamond drilling are being applied in a study to determine the nature of the copper ore occurrences near the footwall of the Osceola lava flow top, commonly referred to as the Osceola Amygdaloid. The work to date suggests that structures formed by relatively impermeable barriers, created by flowage and injection of still-molten lava from the interior of the flow into the solidified, brecciated crust, acted as the ore receptacles. Ascending hydrothermal fluids traveling near the footwall contact were trapped and confined in these barriers which retarded the direct upward movement of the ore fluids and caused deposition of copper. Oreshoots located near the footwall appear to have been formed spatially independently from the hanging-wall oreshoots by fluids traveling simultaneously, but along different channelways. The barrier concept, as advanced by earlier writers to explain the concentration of the ore-bearing fluids into broad shoots constituting entire ore bodies, is found to be equally as applicable for the localization of smaller oreshoots within the Osceola ore body. Recently, the Calumet Division of Calumet and Hecla, Inc. completed the unwatering of the old mine workings on the Osceola amygdaloid. Two shafts were subsequently reactivated and mining commenced on the Osceola lode after an idle period of over 20 years. Early in 1961, the Calumet and Hecla Geological Dept. was assigned the task of locating additional reserves. Accordingly, an intensive mapping and underground diamond drilling program was initiated. Except for a very few years following the first mining on the amygdaloid, the Osceola lode had never been a high grade producer. It was, therefore, recognized from the onset that a concentrated effort would have to be made by the mining, milling, and geological departments to insure success of the project. Company reports contained many references to ore that had been located near the footwall of the Osceola amygdaloid. Information concerning the grade of this ore was meager, but it was known that at least some was very rich. In contrast to ore that occurred near the hanging-wall, however, the footwall copper did not appear to have a systematic distribution and a large amount of poor rock had to be removed in developing this ore. This, of course, resulted in high development costs and discouraged any extensive mining of footwall ore. The possibility of more continuity than had previously been suspected was recognized by other workers, in particular Dr. T. M. Broderick, formerly Chief Geologist of Calumet and Hecla, who suggested attempts be made on a trial basis to follow the footwall contact with the main development drift. As most mining was done on the Osceola lode before a geological department had been established by the company, and almost all of these openings are now caved, very little information concerning the geology of footwall ore was available. It was, therefore, decided that the first step in the exploration program would be to become familiar with footwall ore occurrences by mapping the geology as the openings were driven. It was possible that a mapping program would reveal the features that controlled the localization of the ore. Furthermore, if it could be shown that footwall ore was more continuous, or if its distribution was more systematic than generally believed, it would be possible to produce a high grade ore that could be blended with the lower grade hanging-wall ore. In connection with the geological program, the Michigan College of Mining and Technology Geophysical Dept. under the direction of Professor Lloyal Bacon, is making a geophysical study of the problems of locating footwall ore by electrical methods. GENERAL GEOLOGY OF MICHIGAN NATIVE COPPER DEPOSITS The native copper deposits of Michigan are located in Keweenaw, Houghton, and Ontonagon Counties. The host rocks are Keweenawan in age and are comprised of interbedded sediments and lava flows which form a belt two to four miles wide and over one hundred miles long. These rocks form part of the south limb

Jan 1, 1962

By B. H. Bergstrom, W. Mitchell, C. L. Sollenberger

D. W. Fuerstenau (Associate Professor of Metallurgy, Dept. of Mineral Technology, University of California, Berkeley, Calif.) and D. A. Sullivan, Jr. (with the University of California) — Messrs. Bergstrom, Sollenberger and Mitchell have shown in two excellent papers that the energy per unit mass required for the breaking of spheres is inversely proportional to the size modulus of the fragments of the broken spheres. They found that the fragments of spheres broken within a steel enclosure were finer than those produced by breaking spheres encased in gelatin. This results from utilization of part of the strain energy at fracture for secondary breakage. For spheres not encased in gelatin, these authors found that after fracture the fragments of the spheres possess kinetic energy amounting to 45% of the strain energy needed for initial fracture. Breakage of a sphere in gelatin results in waste of this kinetic energy, whereas breakage inside the steel container makes use of this kinetic energy for further size

Jan 1, 1962

By W. C. Winegard, E. L. Holmes

The effects of the solute elements lead and bismuth on grain growth in zone -refined tin have been investigated. At low temperatures, viz. below 160°C. or at high concentrations, viz. greater than 0.03 at. pct, the temperature dependence of grain growth was found to be constant. A correlation was found to exist between the rates of grain growth in the presence of solute impurities and the factor [C Ir - 1]2 , where C is the solute concentration, r is the radius of solvent atom, and r' is radius of solute atom. It is shown that the Liicke and Detert theory does not give a satisfactory explanation of the results obtained. INVESTIGATIONS of grain growth in zone-refined lead and tin and some effects of solute elements on grain growth in these metals have been reported by Bolling and winegardly2 and Holmes and winegard? The present investigation is an extension of the previous work, and was undertaken to provide additional results which might make it possible to discover the mechanism whereby the rate of grain growth is affected by the presence of foreign solute atoms. The experimental procedure was exactly the same as that described previously.3'4 Figs. 1 and 2 show the results obtained with lead and bismuth additions over the same temperature range, viz. 167" to 220°C, as that used for the investigation of grain growth in zone-refined tin.3 Fig. 3 shows the results obtained for zone-refined tin and for this tin with lead solute additions over an extended temperature range. DISCUSSION OF RESULTS As mentioned previously,3 the character of grain growth in the particular zone-refined tin used in these experiments appears to change as the temperature of annealing falls below about 160°C. The grain growth became somewhat irregular and was characterized by a jaggedness of many of the grain boundaries. The reason for this change is not known, but may be due either to residual impurity effects or possibly an oxide precipitation. It was obvious that normal grain growth only occurred in the zone-refined tin through the high-temperature range 167" to 220°C, and so the effects of solute atoms on grai11 growth over the two temperature ranges will be discussed separately. a) Effect of Impurity on Grain Growth in the Temperature :Range Above 167°C. It is apparent from Figs. 1 and 2 that, for low concentrations of solute, the rates of grain growth tend towards a common value as the melting temperature of tin is approached. As the concentration of lead is increased, the rate of grain growth close to the melting temperature is also reduced, and at high concentrations the temperature dependence of the rate of grain growth appears approximately constant. It should be noteil that the effect of bismuth is greater than that of the same concentration of lead, but both these solutes have a smaller effect on the rate of grain growth than silver, as seen from an earlier investigation of Holmes and Winegard. It should

Jan 1, 1962

By Ralf M. Kleine

THE property of Consolidated 1 Discovery Yellowknife Mines Limited, (Figure I) is situated in the Northwest Territories, approximately 50 air miles north of the town of Yellowknife. The mine is reached by a shaft which extends from surface to a depth of 4,000 feet, with working levels established at 1 50-foot intervals. Stopping operations are carried on throughout a vertical range of 2,000 feet, with both shrinkage and cut and fill methods being used, depending on the ground conditions. Production started in 1950 and milling is done in a 1 65-ton per day cyanide plant. During ten months of the year, the property is serviced entirely by air, utilizing charter aircraft from Yellowknife. A 4,000-foot runway near the mine was constructed from mill tailings. This strip is adequate to receive Bristol freighter planes carrying heavy loads. Other servicing is done by Otter aircraft, equipped with skis or wheels for winter and with pontoons for summer operations.

Jan 1, 1962

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962

By Alla D. Mah

The heat of formation of scandium sesquioxide (Sc203) has not been measured previously, and existing values for gallium sesquioxide (Ga203) are subject to large uncertainties. As a consequence, thermodynamic calculations involving these oxides hare lacked scientific exactness. This paper reports newly determined values of the heats of formation of gallium and scandium sesquioxides at 298.15° K., by combustion calorimetry. The corresponding free energies of formation are derived from heat and entropy data.

Jan 1, 1962

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

By N. S. Kenny, A. A. Burr

THE purpose of this note is to present evidence that vacancies, which have been produced by quenching from a high temperature, alter the rate of strain-hardening of an hep single crystal. The majority of investigations of the effects of quenched-in vacancies on the yield stress of metals have been made using fee samples in the form of thin wires. However, there is an inherent disadvantage in using such wires to study the effects of vacancies on the rate of strain-hardening of metals because fee wires begin stage II slip either immediately upon yielding or very shortly thereafter. When stage II slip occurs, very rapid strain hardening also occurs, masking the effects of vacancies on the rate of hardening. In this investigation single crystals of magnesium hep were studied since magnesium has only one slip plane at low temperatures and has, therefore, an extensive easy glide region. In addition, the effect of both static and dynamic recovery on the rate of hardening were eliminated by testing in liquid nitrogen. Both forms of recovery occur in hep metals by dislocation climb, which is a diffusion controlled mechanism and is negligible at liquid nitrogen temperatures. Finally, the dependence of the strain-hardening rate on the crystal orientation was eliminated by using the equations of Schmid and Boas.' Variations in the strain-hardening rate could, therefore, be attributed to the presence of vacancies. Single crystals in the form of rods approximately 5 mm in diam and 6 cm long were grown by a modified Bridgman technique from commercial high-purity magnesium (99.97 pet) supplied by the Dow Chemical

Jan 1, 1962

By T. D. Tiemann

The caustic extraction of silica from Wisconsin and Minnesota taconite was investigated by bomb digestion over the temperature range from 312 to 40S°F at caustic concentrations from 25 to 500 gpl. Residual concentrates containing as much as 65 pct iron were obtained. The high rate of silica extraction is related to a microcrystalline variety of quartz, since it is shown that the rate of extraction of silica from quartz is directly proportional to its surface area. Increasing dependence on foreign ore reserves makes the need for developing the technology necessary for treatment of our low grade ores even greater than it was at the time of World War 11, when much research was conducted on the extraction of alumina from clays. Representative of these were the studies carried on at the University of Illinois.' More recently, the U. S. Bureau of Mines investigated the production of alumina from anorthosite, and currently the aluminum industry is showing renewed research interest in this field. The studies reported here are part of a continuing research program based on the above concepts and aimed at the eventual development of processes for the treatment of low grade ores, particularly those of iron. The fact that large reserves 3 of low grade nonmagnetic taconite are contained in the iron formation of the Wisconsin Gogebic range have made this ore an important and attractive target for investigation. The idea of removing silica by caustic extraction is not new.495 The digestion in caustic solution of ground flint, diatomite, and other forms of chalcedonic silica is the basis for the production of soluble sodium silicates by the wet-process. Upgrading bauxites by the caustic extraction of silica has been investigated6 and is the subject of a German patent.7 Although mention is made by Roe' of the caustic extraction of silica from low grade Michigan and Wisconsin iron ores, and he lists a number of patents and references on the subject, recent work in the field does not appear to be extensive. As far as the author knows, there has been no work in this field on these particular ores. It is hoped that this paper will stimulate further investigation which will eventually lead to an econclmic means of processing these large low grade reserbes. TACONITES The taconites investigated in this study were from Minnesota and Wisconsin. That from Minnesota, a semi-taconite, Nas obtained from the Oliver Iron Mining Division, U. S. Steel Corporation, and represents a sample of an oxidized iron formation from their King Mine on the Mesabi range. The Wisconsin taconite came originally from the trench sampling of the U. S. Bureau of Mines, and represents a composite of the Norrie, Pabst, Yale, Plymouth, and Pence members of the Gogebic iron formation. Assays on these samples are given in Table I. A typical calcu1atr:d average analysis of the Wisconsin taconite is given in Table 11. Chemically, the Minnesota semi-taconite sample contains about 39 pct iron and 39 pct silica, while the Wisconsin taconite contains 30 pct iron and 53 pct silica, both on the dry basis.

Jan 1, 1962

By J. L. Potter

An inert-gas fusion technique was applied by the Bureau of Mines to the oxygen analysis of mixed-fluoride electrolytes used in electrowinning uranium and the rare-earth metals. Method development included: (1) Thermodynamic and experimental evaluation of the temperature required to quantitatively remove oxygen from a fluoride melt; (2) installation of a water and an acid trap to entrain the volatilized fluorides; (3) development of a suitable sample-preparation technique for the heterogeneous fluoride baths in which both pulverizing and pelletizing were necessary to achieve reproducible results; (4) comparison of platinum flux and dry crucible techniques, which showed that the use of platinum was not necessary. The accuracy of the method was evaluated by analyzing fluoride baths containing known amounts of oxygen added as the metal oxide. In the 0.05-to 0.5-percent range, the relative error was about ±5 percent.

Jan 1, 1962