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By Alfred V. C. Meyer

A Blastcorder4 was calibrated on the Bureau of Mines shaking table in the frequency range of 12 to 40 c.p.s. and in the amplitude range' of 0.25 to 1.0 g. The results of this calibration study show that in the frequency range of 12 to 30 c.p.s. the average accuracy of the Blastcorder is approximately ± 0.1 g.

Jan 1, 1962

By W. A. Calhoun

A method for concentration of the nickel-cobalt-bearing mineral, siegenite, from a table middling has been developed by the Bureau of Mines at Rolla, Mo. The table middling is composed of a complex series of sulfide minerals, occurring in mill operations in the southeast Missouri "lead belt." In these operations the siegenite is lost as a separate concentrate, being diverted to other products. The procedure also includes recovering commercial-grade concentrates of copper and lead. A low-grade zinc concentrate, a potential coproduct, was also made.

Jan 1, 1962

By M. P. McArthur

General mining practices at W. R. Grace's Bonny Lake mine are much the same as those used in open pit phosphate mines in Central Florida, except for the difference in the depth of the overburden which introduces many variations, From 1945 to 1961 the mining at Bonny Lake has been from an area in which the overburden averages from 55 to 60 feet and in several locations exceeded 65 feet. The matrix thickness will average 15 to 18 feet for the areas mined. As you can see from the above depths a total hole depth will average from 70 to 75 feet.

Jan 1, 1962

By Charles O. Frush

This paper presents a summary of the current employment practices with respect to recent graduates in Mining Engineering, as observed at the Colorado school of Mines. Because our experience is limited to our own group of students it prob¬ably does not correspond exactly to that experienced at other mining schools, but because the Colorado School of Mines graduates approximately 15 per cent of the men in this field our experience is probably representative. We have chosen to limit the information presented here to that pertaining to the period since July 1, 1960. This corresponds to the experience with the class of 1961 and to the experience of the class of 1962 up to the end of the first semester of the senior year. There were 36 mining engineering degrees given in 1961 In a class numbering 43 senior. We expect to give 30 first degrees in 1962 in a class numbering 44 seniors.

Jan 1, 1962

By C. G. Bieber, R. F. Decker

The effects of minor constituents on the malleability of nickel alloys are described. These effects are related to the atomic diameter, valence, and position on the Periodic Table. The basic methods for removal or neutralization of deleterious elements are then reviewed. Finally, practical methods for melting nickel alloys are described in detail and related to minor constituent control. L HE first malleable nickel was produced by Fleit-man in about 1870 by the addition of manganese and magnesium to the molten metal to counteract the harmful effects of sulfur. Merica and Waltenbergl explained the mechanism by which these elements accomplished the desired result. They showed that sulfur in concentrations in excess of about 0.005 pct produced films of a brittle low melting eutectic of nickel-nickel sulfide which completely surrounded the grains. When manganese was added to molten nickel it reacted with the sulfur to form manganese sulfide which precipitated as widely scattered globules in the grain boundaries. The further addition of small amounts of magnesium converted the sulfur to a very stable sulfide of magnesium which was relatively insoluble in both the liauid and solid states and therefore occurred as finely divided particles within the grains where it had relatively little detrimental effect upon the malleability of nickel or its alloys. The practice of treating nickel with manganese and magnesium came to be called "deoxidation" and was employed without appreciable modification for the commercial production of wrought nickel and high nickel alloys (in this paper—50 pct or more nickel) until about 1930 even though the results were never entirely satisfactory. At that time a more extensive study was made of the effects of minor constituents on malleability and metallurgical quality. The results, small portions of which have been published,2-4 are presented here with other pertinent data. EFFECTS OF MINOR CONSTITUENTS UPON NICKEL Systematic additions were made of 0.5 pct or less of each of most of the elements of the periodic ta- ble. It was established in this study that some minor constituents other than manganese and magnesium were extremely influential. The malleability, as evaluated by the reduction of area in tension tests, depended roughly on temperature as shown in Fig. 1. Four temperature zones are of interest; the cold malleable zone (up to about 1000° F), the red short zone from roughly 1000° to 1500' F, the hot malleable zone around 2000° F and the incipient melting zone. Most of the malleability problems are associated with the red short zone and the discussion will concern this mainly. The reduction of area in normal tensile tests on high-purity nickel (see curve A of Fig. 1) appeared to have no

Jan 1, 1962

By R. W. Heckel

It has been shown previously that the effect of applied pressure on the density of a metal powder may be expressed by a relationship of the form:

Jan 1, 1962

By Francis J. Kelly

This Bureau of Mines study was made to obtain and present facts concerning the production and marketing of rare-earth metals and thorium in the Central and Southern Rocky Mountains (Arizona, Colorado, New Mexico, Utah, and Wyoming, referred to in this report as the region) and to review the current demand for these elements in the United States. Little or no published information was available on the marketing practices for these commodities. As a result of many inquiries from industry, potential prospectors, and the general public, the various factors of resources, production (present and potential), marketing, and consumption have been investigated, and the results are set forth in this report. Material concerning occurrences and deposits is from published references detailed in the bibliography.

Jan 1, 1962

By W. L. Dare

Tri-axial strains in pillars, created by pillar robbing, were measured in an experiment at the Dysart No. 1 uranium mine near Grants) New Mexico. At this mine, room-and-pillar stoping is used on the advance, and pillars are recovered on the retreat. The are deposit is, for all practical purposes, horizontal. Measuring devices were installed in pillars approximately 90 to 200 feet from the break line, and strains were recorded over a 4-to 6-week period. The measurements indicate that, in general, the algebraic magnitude of vertical strains increased, and the horizontal strains decreased, in turn, indicating that vertical (or near vertical) loads on the instrumented pillars lessened as pillars were recovered.

Jan 1, 1962

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By A. A. Cochran

The purpose of this Bureau of Mines research was to investigate the theoretical and practical aspects of using ionizing radiation to promote chemical reactions that are of interest to metallurgists, and to carry out a radiation study of a suitable reaction. The effect of 44,000 roentgens per hour of 120,000-volt X-rays on the chlorination of highly pure mixtures of rutile, carbon, and various catalysts at temperatures up to 540° C. is described. At these low temperatures, recoveries were very low; however, in the eight different systems studied, an increase in yield due to X-rays was statistically significant in two instances and was of borderline significance in a third instance. In the other five systems, the differences in yield were not significant. Impurities and added catalysts caused relatively large variations in the yield of TiC14 from the reaction. Although the catalysts employed were reported in the literature as positive catalysts for the reaction, most of them were negative catalysts for the highly pure system studied. With only one exception, each increase in the purity of the charge resulted in a decreased yield of TiCl4. The experimental results indicate that many substances catalyze the reaction studied and suggest that the differences in reactivity of the charge stocks may be due to their various contents of positive and negative catalysts.

Jan 1, 1962

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962

By O. P. Arora, M. Metzger, G. R. Ramagopal

The rates of grain boundary and general corrosion were surveyed by an approximate method. Quantitative differences between their variations with the strength or cupric ion content of the acid yielded large variations in their ratio, highly selective intergranular attack being observed only under specific chemical conditions. The boundary corrosion rate increased with the copper content of the aluminum; this was attributed to an autocatalytic effect similar to the one shown for general corrosion. High- purity aluminum in hydrochloric acid exhibits striking intergranular corrosion and other structure-dependent corrosion phenomena of fundamental interest. The behavior is highly sensitive to the metallurgical and chemical conditions, the significance of many of which has not been established. The features of the intergranular-corrosion phenomenon, first described by Rohrman,l are summarized in the remainder of this paragraph. Strong attack normally occurs only at high-angle grain boundaries.' Usually 15 to 25 pctHCl is used to obtain a high rate, but this has also been obtained with weaker (7 to 15 pct) acid either by adding cupric or ferric ion to the acid3-5 or by passing an anodic current (-0.1 ma per sq cm).2,3,5,6 The two latter corrosion conditions produce strong attack of low-angle boundaries after certain heat treatments 2-4,5,7 The susceptibility of high-angle boundaries is influenced by the grain-boundary segregation of iron atoms; this increases the slow (µ per month) attack in 10 pct HCl8 but diminishes the rapid (mm per month) attack in 20 pct Hc14 (the present and most previous investigations deal with rapid attack). That segregation of elements other than iron affects intergranular corrosion has not been demonstrated, although analysis of data for iron alloys indicated that at least one other element must be considered.9 Intergranular attack occurs over a wide range of purity although it begins to become obscured above several hundred parts per million (ppm) total im- purities by the severe general corrosion which accompanies the higher iron contents and which is associated with the presence of a second phase or an inhomogeneous distribution of the dissolved iron.4,6,10 The variation of intergranular-corrosion rate with heat treatment1'3-6'"10 can be explained in some cases in terms of the distribution of the iron impurity but is not in general adequately understood. The present work dealt with two questions not previously considered in detail. The first proceeded from the view that the extent to which a special behavior is associated with the boundaries is indicated not by the intergranular corrosion rate alone but by the ratio of the intergranular to the general corrosion rate. A comparison of the two rates was therefore made for one lot of aluminum in acids of varying strength and metallic ion content. The second question was the effect of the copper content of the aluminum. For general corrosion, it has long been known that copper ions introduced into the acid by corrosion of the solid solution are reduced on the aluminum as patches of elemental copper which enhance the corrosion rate by providing cathodes of lower hydrogen overvoltage than were originally present.''-'3 Since the copper patches remain themselves unchanged, their action is "catalytic", and since they are products of corrosion, the effect is "autocatalytic." This phenomenon is significant at copper levels much lower than previously suspected, even at those typical of high-purity aluminum, as the authors have shown in a previous paper.l4 The present work shows that copper content affects intergranular corrosion. With polycrystalline specimens, truly quantitative rate measurernents are not readily made for intergranular corrosion or for general corrosion in the presence of rapid intergranular attack, and previous work in this field has tended to be qualitative. The present study made use of a simple procedure which provided fair approximations to the quantitative corrosion rates and fitted the purpose of surveying the behavior over % wide range of conditions and displaying certain large effects. The approximations involved in this work were usually outweighed by the experimental scatter, which tends to be substantial in a system as sensitive as this one. I) EXPERIMENTAL A. Material. The material procured, Table I, represented three low copper (1 to 3 ppm) lots, two of "normal" copper content (21 and 22 ppm), and two

Jan 1, 1962

By Roy F. Waters

An inventory was made by the Bureau of Mines of wastes of mineral origin, water requirements, treatment of wastes, and water treatment practice of 163 industrial installations in the Lower Missouri River Basin. This is the second and concluding report on the survey, conducted in cooperation with the Missouri Basin Field Committee of the Department of the Interior as part of the Missouri Basin project. Principal industries covered by this second report are: Sand and gravel, coal, meat, ice, brewing, paint, petroleum, chemical, fabricated metals, and a number of industries having either no waterborne wastes, or none of mineral origin. Gravel, sand, and silt from 47 producers are the major wastes, totaling 6 million tons annually, Coal mine wastes in the form of slurried solids from washing crude coal are second in volume, totaling 100,000 tons per year. They contain an average of about 40 percent coal. Salt is the third largest waste, amounting to 28,000 tons per year, Next is calcium carbonate, most of which is formed in water treatments, Because of its high unit value, chromic acid is important, although the waste quantity is much smaller; cyanide wastes are also significant because large quantities of sodium hydroxide and chlorine are consumed in their treatments prior to disposal. The various industries discharging wastes use 38 billion gallons of water annually; the recirculation rate is 109 billion gallons per year. The plants discharging no waterborne mineral wastes use 2 billion gallons of water per year and recirculate more than 1 billion gallons. Sand and gravel plants use 13.5 billion gallons; petroleum refineries use 10 billion gallons in direct use and recirculate 82 billion gallons per year.

Jan 1, 1962

By K. E. Tame

The Bureau of Mines is studying possible modifications in conventional ore-processing methods that will confine and permit controlled disposal of radioactive liquid wastes. Stream and ground water pollution from radio-active nuclides, principally radium 226 and thorium 230, in liquid wastes from uranium mills can be minimized by reusing the waste solution within the mill. Such reuse of waste solution in an acid leach-resin-in-pulp flowsheet was investigated in the laboratory. The process consists of acid leaching for dissolution of the uranium, sand-slime separation and countercurrent decantation washing for recovery of a pregnant slime slurry, and the use of ion-exchange resin for recovery of uranium from the slurry. Reuse of clarified barren effluent for washing in the simulated mill circuit was carried through 55 cycles. Dissolution of uranium from the ore averaged 97.5 percent. Washing efficiency of 99.9 percent was attained when using 4.35 volume tons4 of combined barren effluent and makeup water per ton of ore. Absorption of uranium from the pregnant slime slurry by an ion-exchange resin averaged over 99.9 percent.

Jan 1, 1962

By J. Robert Wells

The Bureau of Mines has developed a spectrochemical procedure for determining 19 impurity elements in high-purity titanium metal, titanium oxides, and titanium halides in which all samples are converted to titanium dioxide. Determination of these impurities was studied in the general concentration range of 0 to 1,000 p.p.m., but different determination limits were found for the various elements. The procedure is quantitative for 18 elements but semi-quantitative3 for beryllium and has an overall relative standard deviation of 15.8 percent. Two mixtures were used, one composed of graphite and lithium carbonate plus gallium oxide and the other of graphite and lithium carbonate plus germanium dioxide. Each mixture was blended mechanically with an equal weight of titanium dioxide. Lithium carbonate served as buffer-diluent. Gallium was the internal standard for 1 impurity element, germanium for 7, and titanium for the remaining 11.

Jan 1, 1962

By Norman L. Newbern, Robert E. Green

An investigation of the effect of size on the deformation properties of metal single crystals made it desirable to grow from the melt cylindrical aluminum single crystals possessing exactly the same crystallographic orientation but varying in diameter. Methods for the growth of rather large (up to 3 in. diam) aluminum single crystals in molds of the desired shape are well known. However, when one applies the same techniques to the growth of smaller (less than 1/8-in. diam) specimens many additional problems arise. Two of the major problems are the construction of the molds to be used and the removal of the thin specimens from these molds without deformation after growth has been completed. Also the problem of the constraint forces exerted by the mold on the specimen is much more pronounced for the smaller specimens. The technique described herein is a zone-melting method in which no mold is used since the surface tension of the molten metal and its oxide is sufficient to retain the melt. The specimen is suspended vertically in a manner similar to that of Keck and Golay.2 However, while Keck and Golay supported the specimen from both ends, the method used here supports the specimen only at the upper end. The surface tension of the molten aluminum and aluminum oxide contains the melt and suspends a length of newly grown crystal that has already passed through the molten zone until the weight of the newly grown crystal is equal to the component of surface tension holding the specimen together in the molten region. When the weight of the newly grown crystal is equal to the component of surface tension holding the specimen together the specimen pulls in two in the molten zone. The length of crystal which can be grown before this separation occurs varies with the diameter of the specimen and the size of the molten zone. In order to prevent the specimen from pulling in two a tube of glycerine is placed beneath the furnace in such a manner that the newly grown crystal passes into the glycerine which provides sufficient buoyancy to allow aluminum single crystals in wire form to be grown to lengths determined only by the length of the tube containing the glycerine. A schematic diagram of the experimental arrangement is shown in Fig. 1. The furnace used is constructed as follows. High-resistance nichrome wire is coiled on a 3/8-in. diam fused quartz tube. The distance between the windings is much less over a length of about 3/8 in. at the center so as to develop a hot spot. This core is located in the center of a 4-in. diam steel cylinder 5 in. in height and insulated from it by Kayolite. The temperature of the furnace is controlled by means of a thermocouple located near the central hot spot and a Minneapolis-Honeywell temperature controller. Temperature ins,ide the furnace is measured with a thermocouple and a standard potentiometer in the usual manner. By the above method it is possible to grow high-purity (99.99 pct Al) aluminum single-crystal wires over a range of sizes. Crystals varying from 1/8 to 1/64-in. diam were grown by the authors. Since the tube containing the glycerine cannot contain a crystal longer than approximately 3 ft, the growth of crystals longer than this presents another problem. It was found that one could cut the newly grown crystal without deformation in the region between furnace and glycerine tube try means of a cutting torch and then by moving the glycerine tube slightly aside continue

Jan 1, 1962

By W. A. Calhoun

This report gives results of metallurgical investigations performed by the Bureau of Mines on mineral samples taken during April 1959, from Hawaiian bauxite deposits on the islands of Kauai, Maui, and Hawaii. The bauxite samples were tested at the Bureau's Rolla Metallurgy Research Center, Rolla, Mo., to determine if alumina could be extracted. The results were encouraging. Extraction of the alumina by the American Bayer type digest of crude ore samples from Kauai, Maui, and Hawaii recovered 78.8, 73.1, and 70.0 percent, of the total alumina, respectively. These recoveries were increased to 82.8, 85.5, and 79.5 percent by modifying the treatment, which consisted essentially of calcination and weak caustic desilication to provide a residue. The residue was then treated with calcium oxide and digested in a strong caustic solution to extract the alumina.

Jan 1, 1962

By Frank B. Fulkerson

Aluminum production in the Pacific Northwest has a new potential for expansion and increased stability of operation. This new potential results from greater availability of power; lower freight rates on alumina and aluminum; good market prospects for the metal, including western aluminum market expansion following a decline in defense requirements in the 1950's; and possibility of developing bauxite deposits in the Pacific Basin as well as other mineral resources. INTRODUCTION This is a report of a special study by the Bureau of Mines of the primary aluminum industry of the Pacific Northwest. It outlines developments relative to the United States as a whole.

Jan 1, 1962

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By Finley A. Campbell

THE Quemont and Horne mines are located at Noranda in north-western Quebec. As shown in Figure 1, the Noranda area lies between the Cadillac-Bouzan fault zone on the south and the Porcupine-Destor fault zone to the north. Both of these major structural lineaments appear to be geometrically, and possibly genetically, related to the Grenville Front. The regional geology has been discussed by Wilson (12), Cooke et al. ( 2), and others. The geology in the Noranda vicinity, as compiled by Dugas and Gilbert ( 3), is shown in Figure 2. The Cadillac-Bouzan fault zone separates the dominantly Temiskaming-type sediments in the south from the Keewatin-type canic rocks to the north. These volcanics, which vary in composition from rhyolite to andesite, form a broad anticlinorium with a general eastward plunge. A succession of dioritic stocks, sills and dikes have been mapped in the area. The principal granitic rock masses include the Powell, Flavrian and Dufault stocks.

Jan 1, 1962