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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 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 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 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

By W. H. Gauvin, N. J. Themelis

I N ADDITION to its practical importance in the beneficiation of iron ores and in direct-iron processes, the study of the reduction of iron oxides involves many aspects of challenging theoretical interest. The complexity of the reduction process combined with the fact that under different experimental conditions the controlling stage for the reaction may not necessarily be the same, has led experimenters in this field to a wide diversity of opinion regarding the reaction mecl1anism. As a rule, each investigation has been restricted to the study of one or two variables over a comparative]~• narrow range of experimental conditions, and consequently, it be-comes necessary to examine the significance of each published work in the light of the results of other experimenters in the field.

Jan 1, 1962

By Louis P. Domingues

As part of a study on high-temperature ceramic materials, the ammonium sulfate, carbonate, nitrate, oxalate, and sulfate salts of yttrium, lanthanum, and cerium were analyzed thermogravimetrically. The temperature ranged from room temperature to 1,500° C. Each salt was decomposed by heating at a rate of 2.5° C. per minute, and some of the salts were subjected to additional rates of 5° C. per minute or 10° C. per minute. The decomposition sequences have been identified, and the temperatures of formation of intermediate compounds and of the oxides have been determined. The minimum oxide formation temperature of a given lanthanum salt exceeds that for the similar salt of yttrium, and both exceed that for the same salt of cerium except for one cerium carbonate. Variation of the heating rate indicates a thermal lag in the materials and produces the shift of formation temperatures to higher values and loss of resolution in the weight-loss distribution as the heating rate increases.

Jan 1, 1962

By Rodney P. Smith

THE solubility of columbium nitride in ? iron has been determined for the temperature range 1191o to 1336°C from the nitrogen content and metallogra-phic examination of a series of Fe-Nb alloys.* (0.0 to 0.92 pct Nb) equilibrated with a purified gas mixture of 1 pct hydrogen in nitrogen. The method is the same as that used by Darken, Smith, and Filer' to determine the solubility of aluminum nitride in y iron. The variation in the furnace temperature during an equilibration period was about ± 2.0°C. Each sample was approximately 1/2 in. wide, 2 in. long, and 1/16 in. thick. A time series at 1200°C using samples of highest columbium content indicated that one day was sufficient for equilibrium; however, to be on the safe side all samples were left in the furnace for either two or three days. Afterequilibration, the samples were brought to room temperature by quenching in water. The experimental results are shown in Fig. 1. To be in accord with the values reported by Wriedt and Gonzalez2 and the temperature coefficient of our results at higher temperatures, the nitrogen content of iron at 1191oC is assumed to be slightly lower than our experimental value. Our data for the single-phase regions are not sufficiently accurate to establish an interaction coefficient for nitrogen in these alloys. However, the change in nitrogen content with change in alloy content for a number of systems (Fe-N-A1;3,1 Fe-N-Ni;372 Fe-N-Si.3949 Fe-N-V;3,5 Fe-N-Cr;3,6 Fe-N-Mo3,7) has practically the same value for the liquid alloy at a temperature near 1600°C as for the solid alloy at temperatures near 1200oC when the alloy content is below a few percent. On this basis the lines through the single-phase regions have been drawn with a slope corresponding to an increase in nitrogen of 0.0013 pct per 0.1 pct Nb.3 The straight lines through the two-phase regions were drawn with a slope corresponding to a one-to-one atom ratio of nitrogen to columbium in the nitride. The X-ray

Jan 1, 1962

By C. A. Godden, T. N. Atkinson

Metallographic techniques developed from studies of corrosion films and electroplated coatings on aluminum alloys, are discussed. These methods, the result of work at the Naval Research Establishment, give extremely flat fields at the interface despite the large difference in hardness, in cases where electrolytic polishing could not be used. Techniques to overcome the similarity in refractive index of immersion oil, aluminum ox1d~, and mounting plastic are also considered, as are methods for improving visual and photographic contrast in areas of interest. A device for marking specimens is also de-scribed. ELE•CTROLYTIC polishing is inapplicable in the study of surface films on aluminum, whether corrosion films or electrodeposits. Mechanical procedures must there-fore be followed. Sample flatness and edge retention are of paramount importance. Special measures are required in the study of oxide films, because of the close proximity of the refractive indices of aluminum oxide, mounting plastic, and immersion oil.

Jan 1, 1962

By W. M. Tuddenham

It would be most difficult to place a date on the beginning of the revolution in analytical techniques that we have witnessed in recent years; but there is no question that the period since the end of World War II has seen a major change in thinking with respect to control and accounting analyses. For reasons relating to competition, much of this change was brought about in the chemical industries and only more recently has begun to affect directly the mineral industries. In considering the subject outlined in the title of this paper, one might well be tempted to discuss solely the more exotic methods of control and automation which have come into being in the past short while. In this paper, however, an attempt will be made to take a broader view and consider not only the application of newer purely physical methods of control but also those phases of chemical plus physical analyses that have bearing on our industry.

Jan 1, 1962

By Arnulf Muan, Hobart M. Kraner

Ferromanganese alloys react with aluminu-silica brick in blast furnace hearths and cause the formation of new phases with low refractoriness and consequent failure of the refractory lining. The nature of these reactions is explained on the basis of petrographic observations, thermodynamic data, and Phase equilibrium considerations. Animproued hearth design resulted from these findings. The production of ferromanganese in blast furnaces presents many problems which are not encountered in the production of iron in the same furnaces. One of the most serious of these problems is the rapid failure of refractories caused by their reaction with the ferromanganese metal. The present paper describes such a "hearth attack", its symptoms, causes, and cure. Following an introductory discussion of operating practice in ferromanganese blast furnaces, results are presented of a petrographic examination of samples from a furnace which had to be shut down because of refractory failure. The causes of this failure are then analyzed on the basis of petrographic observations combined with thermodynamic and phase equilibrium data available in the literature. The latter type of data were subsequently used as a guide in recommending improvements in hearth designs which have since proven themselves successful in practical operations. I) FERROMANGANESE BLAST FURNACE PRACTICE It is considered good practice to blow in a furnace on iron and operate it in this way for a period of time preliminary to producing ferrornanganese. During this time, iron generally penetrates the bottom refractories six or more feet below the original working surface of the hearth. Not only does this metal pervade the joints to these depths, but the pores of the refractories are usually also filled by molten iron. The high throughput of the iron furnace provides ample heat to maintain a high temperature in the hearth refractories. This, together with a high ferrostatic pressure, causes porous clay brick of the hearth to shrink. During subsequent use of such a furnace in ferromanganese production, the iron in the pores of hearth brick if; replaced to some extent by ferromanganese. The replacement is usually not complete. This is probably due to the lower metal throughput and lower prevailing temperatures resulting from this in the brick of the hearth bottom. When the ferrornanganese furnace is banked—or when the temperature in the furnace falls due to a furnace delay—-manganese oxidizes even though the atmosphere is largely CO. Considerable expansion accompanies this oxidation of manganese from metal to oxide. The hearth refractories are then subjected to the disintegrating forces of the volume expansion. These forces may in extreme cases be large enough to lift the furnace off its mantle supports as was described in a previous paper.' When cooling takes place slowly, however, and the temperature remains at a fairly high level, the refractories undergo fluxing action by the MnO. This latter reaction and the reduction of SiO2 of the clay brick is the general subject of the present paper. The observations to be described herein were made on a ferromanganese furnace located at the Johnstown plant of Bethlehem Steel Co. The furnace was lined entirely with clay refractories and had operated on iron for 266 days and on ferromanganese for 96 days prior to being taken off because of a hearth wall failure. II) PETROGRAPHIC EXAMINATION AND CHEMICAL ANALYSIS The photograph reproduced in Fig. 1 shws a cross section of the upper part of an 18 by 9 by 4-1/2 in. bottom block removed from the blast furnace. This brick came from a depth of approximately 6 ft below the original working face of the bottom. It will be noted that the 4-1/2 in. dimension is almost the same as when the brick entered the furnace. Three characteristically different zones marked I, II, and III on the print of Fig. 1 are apparent. Results of chemical analyses of the original brick and samples from each of these zones are listed in Table I. Petrographically the various zones were characterized as follows: The central zone marked I was essentially un-reacted brick. The microstructure consisted of fine needles of mullite, and the pores in this entire area were filled with iron. This is characteristic of

Jan 1, 1962

By A. Michalkow

DELN ITE Mines Limited is located in Deloro township, on the west end of the south break of the Porcupine Camp. Mining operations are currently being carried out on the downward extension of a system of quartz veins in an andesite zone. This zone has been followed from surface to the present bottom level of 5,250 feet. The changing mineralogy of the vein system has involved an increase in tourmaline content from the surface downwards, so that the veins at the lower levels are composed of dark brown quartz-tourmaline. The drilling problem presented by these extremely hard veins was partially alleviated by the development and adoption of a one-inch drill bit. All blast-hole drilling is now done with the one-inch bit, without any difference in hole spacing.

Jan 1, 1962

By Harry Perry

Although the markets for coal in the United States have changed rapidly over the last three decades, the uses of coal, namely, to produce heat and power or coke have been left almost unchanged. The coke is used either as a chemical reducing agent alone or as a reducing agent and source of heat. Most of the heat and power markets for coal require no coal processing, although for more than 50 years, many proposals to skim the more valuable substances in coal before burning have been advanced. Thus, the only large tonnage market requiring processing of coal is high-temperature carbonization to make coke. At present, coal requires processing for some small markets, but for future potential large markets, such as gasification, conversion to liquid and gaseous fuels, and conversion to chemicals, coals will require more processing than is now being done.

Jan 1, 1962

By Joseph Grumer

Theory pertaining to the exchangeability of fuel gases on appliances has been extended to exchanges of propane or butane with mixtures of these. In particular, new considerations were developed bearing on the hazard of an occasional emission of carbon monoxide and flashback and blowoff possibilities. The new considerations involve using current requirements for approval of liquefied petroleum gas appliances. These requirements were used to predict allowable tolerances in chemical composition of liquefied petroleum gases for existing appliances. In addition, changes in gasline pressure were computed which may be substituted in place of fuel exchanges during testing of appliances,

Jan 1, 1962

By R. P. Marshall, L. P. Costas

The solid solubility of lithium in aluminum was determined by two independent techniques, electrical resistivity and microhardness, and the results are in close agreement. The solubility limits X-ray diffraction studies of the intermetallic compound LiAl indicate that its composition is nearly independent of temperature when in equilibrium with the terminal solid solution of aluminum. THE investigation of the aluminum-rich portion of the aluminum-lithium system at the Savannah River Laboratory was prompted by the observation that over-aged alloys consistently differed from the equilibrium states predicted by the latest published diagrams. Chemical analyses of these alloys showed their impurity contents to be quite low; therefore, the results obtained should have very nearly coincided with true equilibrium. A survey of the literature disclosed that previous studies had been made with metallographicig or electrical resistivity methods,4'5 but that agreement between results and technique was poor as evidenced in Fig. 1, which also includes the present results for comparison. The discrepancies have been attributed to impurities,3 and this is undoubtedly true in the early work.1'4'5 The latest Studies,''~ conducted with starting materials of higher purity, employed metallographic analysis, a technique that is quite sensitive to local homogeneity and depends strongly on subjective interpretation. In the present work the problem of defining solubility limits was approached in two ways. The first measured a physical property, electrical resistivity, at the equilibrium temperature. The second, a micro-hardness characterization of a diffusion zone, is a room temperature evaluation of a mechanical property under conditions removed from equilibrium. A close correlation between two such basically different approaches would strongly justify confidence in the results. I) MEASUREMENT OF SOLUBILITY OF LITHIUM IN ALUMINUM BY ELECTRICAL RESISTIVITY Experimental Procedure. Alloys for electrical resistivity measurements were made by melting and

Jan 1, 1962

By Werner Schwartz, Wolfgang Haase

Lead sulfide concentrates, which may include other lead concentrates, are sintered on an up-draught sintering machine without the addition of any diluting agents or fluxes. Subsequently they are melted in an oil- or gas-fired rotary furnace. The sintering and melting processes are based upon the following roast-reaction: PbS + 2 PbO = 3 Pb + SO, PbS + PbSO, =2 Pb + 2 SO, For obtaining a lead bullion free from sulfur, the sintering process is carried out in such a way that the sinter product contains a small amount of excess oxygen above that to react with the sulfides. At the end of the melting process, when the reactions are finished, the remaining small amount of oxide residues is reduced with coal to which a certain percentage of soda ash (about 1 pct of the lead bullion) is added. For the lead smelting process described neither coke nor fluxes—except soda ash—are required. This process is being utilized by a European smelter successfully and with a high lead recovery. The consumption figures for the smelting of 100 tons per day of lead concentrates are indicated. The lead content of the lead concentrates from modern ore dressing plants ranges from 65 pct to above 80 pct. In most lead smelters of the world these concentrates are smelted in a blast furnace. For blast-furnace smelting the concentrates have to be desulfurized and agglomerated by sintering. A requirement for the perfect operation of a down-draught sintering machine and of a blast furnace is a maximum lead content in the feed of 40 to 45 pct. For this reason, some lead concentrates have to be diluted by adding return slags, limestone, and possibly iron oxide and sand. As an example, 100 tons of lead concentrate with 72 pct Pb would contain 13.5 tons of gangue (including the zinc). To produce a perfect sinter with 42 pct Pb it would be necessary to add 70 tons of flux and return slag, more than five times the original weight of the gangue, to the sinter mix and blast-furnace charge. A correspondingly large amount of coke would be required in order that all of these materials reach the heat of formation and the melting temperatures of the slag (1200" to 1400°C) inside the blast furnace. The roast-reaction process presents a possibility for lead recovery without dilution of the concentrates. In this process the concentrate mixed with coal is placed upon a Newnam-hearth and air is blown through nozzles into the heated mix. AS a result metalllic lead and a relatively great amount of so-called .'Grey Slag" with a lead content of 25 to 35 pct are formed. The slag is sintered to eliminate sulfur and, after addition of the requisite fluxes, treatt:d in a blast furnace. Owing to the poor recovery of lead from the hearths and to the unavoidable heavy hand-work plus the risk of poisoning this process is utilized in very few 112ad smelters today. Since in mxny countries of the world coke is expensive and difficult to obtain, it appeared feasible to use the principle of the roast-reaction by modern sintering and melting methods with recovery of the lead in electric, or oil, gas, or coal-fired furnaces. Two processes are utilized on an industrial scale: A) Lead smelting in the electric furnace of the Bolidens Gruv A/B in Sweden, as described by S. J. Walldcn, N. E. Lindvall, K.G. Gorling, and S. Lundquist. B) The self-fluxing lead smelting of Lurgi Gesell-schaft fiir Chemie und Huttenwesen m.b. H., Frankfurt a M, Germany, which is described in this paper. In the Boliden process referred to above the sinter mix is pelletized by enveloping return fines with layers of flue dust, limestone powder, and dried galena concentrate. The roasting and agglomeration are carried out on a down-draught machine, and a slight excess of sulfur is left in the sinter product. During the smelting in the electric furnance the roast-reactions occur and a slag poor in lead and a sulfur bearing lead are formed. This latter is subsequently oxidized in a converter to obtain lead bullion and dross. The Lurgi-process achieves the maximum possible extent of the roasting reaction on the sintering machine. The wet flotation concentrates are blended with return fines (lead content 70 to 80 pet), any existing flue dusts and lead slimes—but without the

Jan 1, 1962

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

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By M. T. Smith

In a 2,000 square mile area of Polk, Hillsborough, Hardee and Manatee Counties in Central Florida is located one of the richest known deposits of the life-giving mineral, phosphorus. Under layers of sand and clay are found millions of tons of phosphate rock, best source of this element which is necessary to all forms of life - plant, animal and human. Phosphorus is an irreplaceable ingredient in all complete plant foods, and more than 90% of Florida&apos;s vast production goes to enrich the croplands of the United States and many other areas of a hungry world. In addition to this, it has wide industrial use in the manufacture of many products - detergents, baking powder, carbonated beverages, steel, matches, munitions, glass, insecticides, dyes, water softeners and innumerable others. Not only does phosphorus make life possible for us - it also helps us to live longer and better.

Jan 1, 1962

By Michael G. Zabetakis

Investigation of gas explosions usually reveals that the combustible gases have come from transmission and storage facilities or from natural gas or oil wells. However, combustible gases such as methane and hydrogen can derive from biological processes. Hazardous situations have been created in the past by the use of abandoned mines for the disposal of sewage and rainwater, by the interconnection of storm and sanitary sewers, by sealing the openings in manhole covers when repaving the roadway over a sanitary sewer, and by the construction of buildings over or near garbage fill areas without adequately providing for the release of combustible gases.

Jan 1, 1962