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By R. P. McNitt

TITANIUM hydrides have received considerable study in recent years because of the adverse effects of the hydrides on mechanical material properties such as ductility and tensile strengths. Generally speaking, as the hydrogen content increases, ductility and strength levels decrease. While the amount of hydrogen present in commercial titanium is negligible, hydrogen may enter the material during welding, electroplating, and so forth. The hydrogen will then precipitate, in the form of titanium hydride. If the material

Jan 1, 1968

By B. F. Oliver, C. W. Haworth

Pure tin and Sn-0.5pct Pb ingots have been frozen unidirectionally from the base. For quiescent melts that were initially undercooled, a transition from lower eqlciaxed structure to an upper columnar structure is found in the alloy ingots. Columnar to equi-axed back to columnar transitions are observed in superheated alloy ingots, but no such equiaxed band is observed impure tin. The reproducible equiaxed band is associated with a thermal undercooling followed by a recalescence. This undercooling is <5"C, whereas the critical (maximum obtainable) under-cooling for both the pure tin and the alloys used is -20°C. A similar undercooling is observed at the same position in the pure tin ingots, although in this case no clear transition in structure can be seen. The structure of the pure tin ingots is either entirely columnar or mixed columnar-equiaxed. A consideration of the detailed thermal history of the ingots indicates that the ingot macrostructures are determined by the occurrence of a local therlnal undercooling in conjunction with nuclei multiplication and transport mechanisrris. GENERALLY it is found that a pure metal ingot solidifies so as to produce an entirely columnar structure. Frequently an alloy ingot is found to have a columnar outer zone and an equiaxed central portion. Early systematic work to examine the factors controlling the formation of the equiaxed structure was reported by Northcott&apos; who showed that, for copper alloys frozen unidirectionally with a given ingot practice, the alloying element influenced the length of columnar crystals and the extent of the equiaxed structure. Northcott showed that alloys with a wider freezing range more readily produced the equiaxed structure. The nucleation process can be important in producing equiaxed structures; frequently an alloy which readily solidifies with an entirely columnar structure will produce an entirely equiaxed structure when a nucleating agent is added to the melt.&apos; The formation of the equiaxed structure was attributed by Winegard and chalmers3 to the presence of constitutional supercooling; that is, a region of liquid in front of the growing solid could have a temperature below its equilibrium liquidus temperature. Thus, with a small enough temperature gradient in the liquid, it was suggested that the presence of constitutional supercooling may be sufficient to bring about the nuclea-tion necessary for the formation of an equiaxed structure. Although this explanation is plausible, and may be relevant in many ingots, Walker has described an experiment&apos; for which constitutional supercooling seems to be an unlikely cause of nucleation. A Ni-20 pct Cu alloy, repeatedly undercooled more than 50"C, was crystallized and found to show the typical colum-nar-equiaxed structure. The separation between the liquidus and the solidus for the alloy is 40°C. Thus, in this experiment the nucleation required for the formation of the equiaxed structure must have come about in some other way than by the nucleation catalysis constitutional supercooling hypothesis. Chalmers has suggested more recently5 that nuclei (in a typical ingot) are present immediately after pouring and are prevented from redissolving by the constitutional supercooling effect. More recently Uhlman, Seward, Jackson, and ~unt&apos; have shown direct evidence using ice and organic materials that freeze dendritically that the "remelt mechanism" may be an extremely effective crystal multiplication process during the freezing of ingots under conditions involving dendritic growth. JSlia" experimentally demonstrated the detachment of dendrite arms. chernov14 has analyzed the dendrite arm detachment process as a coarsening phenomena driven by the minimization of interphase area. Katta-mis and ~lemings" working with undercooled steel melts give evidence supporting this mechanism. Mechanisms of dendrite arm detachment such as those assisted by convection are believed to be the origin of the macrostructures obtained in this study. This study makes no attempt to distinguish the relative contributions of these mechanisms. The object of the present work was to obtain accurate temperature measurements during the solidification of an ingot and to correlate these measurements with the formation of equiaxed grains in the resulting ingot structures. Similar previous work is very limited. The measurements carried out by Northcott are neither sufficiently extensive nor sufficiently accurate for any interpretation. Plaskett and winegard7 carried out experiments on A1-Mg alloys in which they observed values of the temperature gradient, G, in the liquid and rate of freezing, R (for a given alloy solute content Co), at the transition from a columnar to an equiaxed structure. They reported that equiaxed crystals were produced at values of G/G approximately proportional to the solidus composition. Similar experiments using Pb-Sn alloys carried out by £111011" showed a linear relation between G/R and the solidus composition. However, the thermocouples were in the mold wall rather than in the melt and, in one case, ingot surfaces were examined. There is ambiguity in the meaning of the values of G and R measured in all these experiments. APPARATUS AND EXPERIMENTAL PROCEDURE Alloys were prepared by induction melting 99.999 pct Sn and 99.999 pct Pb to form a Sn-0.5 wt pct Pb alloy in air in a graphite crucible and casting into a cylindrical graphite mold 6 in. long, 1 in. in diarn , and with a & in. wall thickness. This mold was mounted on a copper base through which cooling water could be

Jan 1, 1968

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By D. R. Cook, W. M. Shepard, H. T. Morris

The East Tintic district in central Utah has produced ores of gold, silver, copper, lead, and zinc valued at more than $120,000,000. All of this ore has been produced from blind ore bodies in Paleozoic sedimentary rocks that are concealed beneath hydrothermally altered volcanic rocks and cut by intrusive bodies of Eocene age. The Paleozoic rocks, which range in age from Early Cambrian to Mississippian form the core and limbs of a large, northtrending asymmetric anticline that is cut by low-angle thrust faults, high-angle transcurrent faults, mineralized fissures and faults, and normal faults that are both older and younger than the mineralized fissures. The ore bodies generally may be grouped into two classes: ( 1) massive replacement bodies that are rich in silver, lead, zinc and manganese and (2) fissure veins that are valuable primarily for their content of gold, copper, and silver. The replacement ore bodies are localized chiefly in the Middle Limestone Member of the Ophir Formation of Middle Cambrian age where it has been thrust-faulted against older or younger rocks and cut by northeast-trending mineralized fissure zones. The fissure veins primarily are productive only in the Lower Cambrian Tintic Quartzite. Extensive lowgrade deposits of lead-zinc-silver ore recently have been discovered in Devonian carbonate rocks in the Lower plate of the East Tintic thrust fault but as yet are unevaluated. The principal guides to ore include: ( 1) intersections of northeast-trending fissures and crossbreaking faults that brecciate the carbonate rocks; (2) zones of late-stage pyritic, calcitic, and sericitic alteration in the lavas; ( 3) primary geochemical anomalies in the altered rocks; and ( 4) mineral zoning patterns of the known ore bodies. The present development of the Burgin mine would seem to assure the continued productivity of the district for at least a decade.

Jan 1, 1968

By Nelson C. White

This paper summarizes the present state and future prospects of the potash industry, with special reference to its impact on production in Saskatchewan.

Jan 1, 1968

By Charles H. Grant

Communications in whatever we do, is one of the major problems we encounter. In an effort to provide a better understanding of the use of explosives, I am going to take a little different view of what explosives are, and how you might look at them as tools to fragment rock, and some of the problems encountered in doing so. First, let&apos;s take the explosive, and although there are many factors involved, I want you to consider these as being reduced to only two--shock strain imparted to the rock by the high early development of energy; and the other, the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc..

Jan 1, 1968

By A. Kaufman

More than 3 trillion gal of water are used annually by the mineral industry. Of this, approximately 21/2 trillion gal are recirculated, the rest constituting intake water. The major users are natural gas processing plants and phosphate rock, sand and gravel, and iron ore producers. Water was used by the mineral industry for mining (6%), processing (64%), cooling and condensing (27%), and miscellaneous uses such as boiler feed and sanitary purposes (3%). Whereas total water use is dependent on the quantity of material processed and on the particular process requirements of an industry, recirculation is dependent on processing, as well as cooling and condensing requirements, quality of new water intake, and the necessity for treating new and discharged water. Consumed water, on the other hand, is dependent on the quantity of water recirculated, and temperature and humidity in the area. Based on this analysis, an increase in water use by the mineral industry of 21/2 times by 1985 is forecast. Wster intake, however, will only rise 62%, because of a substantial increase in recirculation. In one report of a special series concerning the water resources of the United States, the Senate Select Committee on National Water Resources, 87th Congress, estimated that water demand would double by 1980 and triple by 2000.&apos; In view of the possible water deficiencies that might result from such expanded usage and the need for research guidance, the Bureau of Mines organized and carried out a statistical canvass of water use in the mineral industry for calendar year 1962. The data used in this paper, unless otherwise noted, are derived from that canvass.&apos; The efforts in this paper are devoted toward summarization of the canvass and analysis of the data. SOME DEFINITIONS Intake: Water introduced from an external source for the first time into a given mine or plant regardless of quality. Intake water is also called new water, water withdrawn, or makeup water. Fresh Water: Water suitable for cooking and drinking. Saline Water: Water containing more than 1000 parts per million of dissolved solids. Contaminated Water: Water not suitable for domestic use, but excluding saline water. Recirculated Water: Water reused to conserve intake water. Solutions that are recycled primarily because of fixed metallurgical practices, such as copper leaching solutions containing sulfuric acid, are excluded. Gross Water Used: Recirculated water plus intake water. Also called total water used. Consumed Water: Water that is lost by evaporation, as well as water lost in product. Seepage and transferred water are not considered consumed. The use of either intake or recirculated water may result in consumption. However, because of difficulties in measuring consulmption, consumed water is defined as the residual between intake and water discharged from the mine or plant. Mineral Industry: For the purposes of this paper, mineral industry includes all metal and nonmetal surface and underground mines and their associated processing plants, as well as custom mills, coal washing plants and associated mines, petroleum and natural gas well drillers, natural gas processing plants, and secondary recovery operations. WATER USE IN THE MINERAL INDUSTRY Water used by the mineral industry constitutes a relatively minor fraction of the water withdrawn by all users. Data compiled by the U.S. Geological Survey in 1960 indicate that water withdrawals, exclusive of that used to generate hydropower, approximate 99 trillion gal annually.3 Our data indicate that water withdrawals by the mineral industry comprise only 1% of this total, or 2% of the water withdrawn by industrial users. Use by Industry: Water used by various mineral industries is shown in Table I. The table indicates that close to one-half of the gross water used by the mineral industry in 1962 was used by natural gas processing plants, followed by sand and gravel, phosphate rock, and iron ore producers. The largest aggregate users of water are also the largest users per dollar of product. For example, Fig. 1 shows that the natural gas processing and phosphate rock industries are very large users of water per dollar of product. Their recirculation per

Jan 1, 1968

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors&apos; conclusion.

Jan 1, 1968

By Andrew J. Fergus

A study of the flotation characteristics of columbium-tantalum minerals was made by contact-angle and microflotation methods, and the findings were confirmed by flotation of two natural ores. In the contact-angle study conditions for collection of columbite, pyrochlore, and tantalite were determined for (1) sodium oleate with a sulfonate; (2) sodium isooctyl phosphate; (3) a short-chain primary amine; (4) a long-chain primary amine; and (5) a quaternary amine. These conditions were confirmed in microflotation tests. Information about collector action on common gangue minerals was also obtained by these two methods. In batch flotation tests on a pyrochlore ore and a columbite ore, it was demonstrated that collectors selected on the basis of contact-angle and micro-flotation studies would float columbium minerals from a complex natural ore. However, multiple cleaner and scavenger flotation steps will be necessary to produce commercial concentrates. From a pyrochlore ore containing 0.54 percent Cb2O5, a 44.4 percent Cb2O5 concentrate was made containing 36.4 percent of the total Cb2O5. For a columbite are the corresponding values were: 4.35, 54.6, and 67.1 percent. During the batch flotation study, wetting agents were found to aid in the gangue-ore mineral separations.

Jan 1, 1968

By David W. Wisecarver

Kennecott Copper Corporation and the U. S. Bureau of Mines cooperated in a full-scale slope stability research project at the Kimbley Pit near Ely, Nevada. The west wall of the Kimbley Pit was mined from an over-all slope angle of 45° to an over-all slope angle of 57° and the pit was deepened nearly 50 feet. Mining was begun February 10, 1966, and completed October 30, 1966. Approximately 2.55 million tons of ore and waste were mined. The project was designed and carried out to learn more about the behavior of a pit wall as its slope angle is steepened and to obtain a possible insight into engineering parameters for use in design of future slopes. Data from this project are presented as obtained from (1) instruments installed in two adits for deformation and displacement measurements, (2) a subsidence network installed on the surface above the steepened wall, (3) pre- and post-mining observations of stress in rock, (4) sonic-velocity measurements, and (5) seismic and microseismic investigations. Changes occurred in measured quantities as the slope was steepened but stopped when mining was completed. Agreement was noted between the measured changes and predicted changes obtained from calculations using the finite element technique. Subsidence surveys and microseismic studies show the steepened pit wall to be stable.

Jan 1, 1968

Jan 1, 1968

By R. V. Mrazek

The heat of formation of vanadium trichloride was determined at 298.15° K. Measurements were made in a solution calorimeter in which an aqueous hydrochloric acid-potassium dichromate solvent was employed. Data are presented for the heats of solution of vanadium trichloride and the vanadium trioxide "backup" compound, and for appropriate dilution reactions needed to preserve stoichiometry. The resulting heat of formation of vanadium trichioride (VCI3) at 298.15° K was found to be ?H°298.15° K = -138.89 ±0.37 kcal/g mole.

Jan 1, 1968

By R. W. Ballmer

Bingham Canyon lies in the heart of the Oquirrh Mountains, 25 miles southwest of Salt Lake City, Utah. In it is located the world&apos;s largest open-pit copper mine, owned and operated by the Utah Copper Division of Kennecott Copper Corporation. From the beginning of open pit mining operations in 1906 until 1963, the pit haulage, or materials transportation, was primarily by rail. In 1963, phase-in of a truck haulage system in the upper two-thirds of the pit was begun. The details of that conversion, its associated problems and the resulting pit operation have been covered in an earlier paper.1 The purpose of this paper is to discuss various factors for consideration in transportation system selection, and to discuss some of the alternatives considered prior to making the change from rail haulage to truck haulage for a portion of Bingham Canyon.

Jan 1, 1968

By Jan M. Mutmansky

A knowledge of rock characteristics forms the foundation for the application of rock mechanics to engineering works. Hence, there has been an increased interest in the determination and proper utilization of rock properties data. Most numerical values quoted for rock properties are obtained from arbitrary tests and are not necessarily indicative of any intrinsic rock characteristics. Recent attempts to correlate these properties by statistical methods have attracted considerable attention, in the hope that these might give some clue to the fundamental properties. To date, correlation and regression techniques have been employed for this purpose. The use of statistics has also been deemed appropriate because of inhomogeneity and anisotropy in rocks. The problems have been further compounded by the lack of standardized methods of measuring rock properties. The various ASTM committees are still deliberating on these matters, but recommendations should be forthcoming in the near future. As more reliable data become available, the ability of geoscientists to find more meaningful relationships between rock properties will be greatly enhanced. The objective of this paper is to outline another statistical technique which might be useful in providing an insight into the relationships that exist between rock properties. This method does not attempt to predict rock characteristics, but rather compares the similarity or dissimilarity between properties. This enables rock properties to be classified into groups with similar intrinsic characteristics. The technique described is one form of factor analysis. It allows the results obtained to be depicted geometrically, so as to make ready visual examination possible.

Jan 1, 1968

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum&apos; of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have&apos; any appreciable absorption in the short or long uv regions. When P0&apos;t3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.&apos;-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU&apos;3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total&apos; band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By N. A. D. Parlee, I. D. Shah

ThIS reports on some work done on the solubility and diffusivity of oxygen in liquid silver. Solubility. Improvements in the measurement of the solubility of oxygen in silver and silver alloys were made because precise data were needed for calculating diffusion coefficients of oxygen in these alloys. The apparatus and the procedure used were similar to those of Parlee and Sacris.&apos; The main improvement was in the temperature-measuring technique. A MV30 mullite protection tube containing a calibrated Pt-Pt, 10 pct Rh thermocouple was inserted in the reaction tube from the top through a vacuum-tight swage-lok fitting. The protection tube was well-immersed in the liquid silver, which was heated by induction. A Leeds and Northrup potentiometer was used in connection with the thermocouple. All runs reported were made at 1 atm. The temperature range investigated varied from 940" to 1200°C. The ternary point in Ag-0 phase diagram2 is at 939°C and 0.32 wt pct O. This point was reinvestigated using the above-described apparatus and was found to be at 939°C and 0.315 wt pct 0. It was determined by observing the sudden evolution of oxygen at this point while the solubility measurements were made. The point was easily reproducible if precautions were taken to keep the liquid silver essentially in equilibrium with oxygen and to lower the temperature very slowly. All of the results of this new solubility investigation are plotted in Fig. 1. They are represented by the "least-squares" line shown in the figure and the following equation for solubility at po2 = 1 atm: log% O =695.4/T - 1.086 This equation differs only slightly from that proposed by Parlee and sacrisl and that of Diaz, Masson, and Richardson.3 The points of Parlee and Sacris, using an optical pyrometer, are shown for comparison.

Jan 1, 1968

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,&apos; the gold film marker of Kofstad and ~jijllesdal,&apos; and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.&apos; reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By George E. Summers

A salt dome appears to provide the basic medium requirements for the excavation of the 315 foot diameter, unsupported spherical cavity at a depth of 2700 feet required by the AEC in a proposed "decoupling" experiment. Tatum Salt Dome was a natural choice for a site because more geological and hydrological information has been accumulated on Tatum than any other salt dome on the Gulf Coast. The Tatum Dome is a mile in diameter, roughly flat topped, nearly cylindrical in shape and has some overhang at the top. The salt stock has nearly vertical layering of alternating bands of salt and anhydrite. In the vicinity of the dome, adequate fresh water for solution mining is available in surface streams and in subsurface aquifers. A saline aquifer is available for brine disposal. A tentative cavity location was selected near the center of the dome which meets the design criteria established by the AEC.

Jan 1, 1968

By Basil Dimitriades

Five recently developed methods for determining nitrogen oxides in automotive exhausts have been evaluated from the standpoint of accuracy and applicability in current exhaust studies. Results showed that methods requiring conversion of nitric oxide to nitrogen dioxide as a part of the analytical procedure are subject to errors introduced by the instability of NO2. The extent of some of these errors has been determined and procedures have been developed to minimize undesirable influences. On the basis of the results obtained from this study, recommendations are made regarding procedures for batch type or continuous measurement of nitrogen oxides in exhaust streams.

Jan 1, 1968

By Richard L. Ash

7.3-1. Introduction. All phases of mining competent materials are affected directly by the results achieved from primary blasts. It is imperative that their design suit each particular set of mining conditions. In general, the round design must provide an adequate tonnage of material, properly placed with suitable fragmentation, to ensure that loading, haulage, and subsequent disposal or processing are accomplished at the lowest possible cost. Blasting rounds are designed by the proper application of cratering relationships developed for the single, concentric, confined explosive charge. Blasting for surface mining and most open-cut heavy construction, however, is characterized by the use of rounds, composed of a number of explosive charges with relatively long lengths, which are placed in benches with specific finite dimensions. Therefore, modifications must be made to the classical, single point-charge cratering concepts. It is the purpose of this discussion to outline the basic principles, significant variables, and procedures for their integration in the design of rounds that are applicable to conditions characteristic of surface mining. Because relatively insensitive blasting agents will be used in most instances, particular attention must be given to priming, control of confinement, and selection of charge diameters that ensure complete explosive-reaction execution. 7.3-2. General Considerations. The primary requisites for any blasting round are that it ensure optimum results for existing operating conditions, possess adequate flexibility, and be relatively simple to employ. It is important that the relative arrangement of blastholes within a round be properly balanced to take advantage of the energy released by the explosives and the specific properties of the materials being blasted. There are also environ- mental and operational factors peculiar to each mine that will limit the choice of blasting patterns.

Jan 1, 1968