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By U. Storck

"Shaft sinking for exploitation of the deep potash beds in Saskatchewan involved great difficulties from the very first because of the need to exclude from the shaft the high-pressure water encountered in the overburden. Control of the troublesome Blairmore quicksands was achieved relatively quickly by use of the freezing method and by lining with cast iron tubbing. The unsolved problem remained, however, of sealing the water-bearing Devonian where the formations had extremely low permeability and were thus hard to grout. Long experience in German potash mines had shown that the permanency of the whole mine would be seriously endangered if large amounts of unsaturated salt water were allowed to flow in from the shaft wall and merely removed by pumping. The prevention of water movement and the resulting dissolution of salt in the overburden were known to be most important. In the Alwinsal shaft, water flow from the Devonian has been prevented by the use of a steel and concrete sandwich lining similar in principle to a kind of lining introduced a few years earlier, and for another reason, in German coal shafts. As its installation is neither more expensive nor more time consuming than that of cast iron tubbing lining, this same lining was also chosen as protection against the Blairmore quicksands. The great advantage of the steel lining, in addition to its relatively high strength, is the fact that it is possible to make the joints of the individual segments absolutely and permanently water-tight by means of tested welds. The virtual dryness of the Alwinsal shaft will also result in lower costs because significant corrosion of all its steel installations, including skips, cage and ropes, will be prevented."

Jan 1, 1968

By E. H. Phillips, A. F. Keenan

6.2-1. Historical Development. Hammering on hand-held drill steel was the earliest type of percussion drilling. It was not until 1838 that Singer developed a steam-operated drilling machine that lifted a drilling bar and let it drop by gravity. J. J. Couch of Philadelphia patented the first percussion drill in 1849. His machine was a steam drill which literally hurled the drill bar at the rock and retracted it by means of a ratcheted wheel. Later J. W. Fowle added automatic rotation of the steel. In 1871, Simon Ingersoll patented a rock drill mounted on a tripod which permitted drilling holes at any angle, vertical to horizontal. Up to the turn of the century, percussion drills in use were piston-type drills. The drill steel was solid and attached to an extension of the drill piston. Hole cleaning was accomplished by the pumping action of the steel in the hole. Down-holes were drilled wet and cleaned with a blow pipe while up-holes were drilled dry, allowing the cuttings to drop out by gravity. The forerunner of our present hammer drill was the free-piston drill which was first patented in 1884, by Sargent. Because solid drill steel was used, it did not successfully clean down holes. J. G. Leyner solved the problem of applying the hammer drill principle to down-hole and horizontal-hole work in 1897. The key was to pass com- pressed air and water through hollow drill steel to clean the hole. Leyner's work on valves and rotation mechanisms increased the blows per minute of hammer drills from 300 or 400 up to 1800 and more blows per minute and made possible the first lightweight drilling machines. The development of automatic feeds followed. 6.2-2. Percussion Drills. TYPES OF DRILLS. There are two types of percussion drills in use today; the piston drill and the hammer drill. In the

Jan 1, 1968

By Richard A. Dick

In this report commercial blasting compounds are classified according to their nitroglycerin (or equivalent explosive oil) and ammonium nitrate content as dynamites, gelatins, blasting agents, military explosives, and blasting , accessories. The ingredients and more significant properties of each explosive are tabulated and briefly discussed. Data are summarized from various handbooks, textbooks, and manufacturers' technical data sheets, together with the author's personal experience; however, this report is not intended to be a technical handbook, since it does not deal with blasting techniques. Instead, it seeks to acquaint the reader with the great variety of explosives, available, their advantages and disadvantages, and their general areas of application. Properties discussed are weight strength, cartridge strength, detonation velocity, density, detonation pressure, water resistance, and fume class. The weakness of the strength rating system and the importance of detonation pres- , sure, density, and detonation velocity in rating explosives are discussed. The terms "blasting agent" and "slurry," which are often misused, are defined. Trends indicate that blasting agents (that is, blasting mixtures with none of of the ingredients singly classified as an explosive), particularly high-density slurry blasting agents, will dominate the explosives field in the future.

Jan 1, 1968

By J. L. Reuss

The Bureau of Mines investigated the technical feasibility of smelting copper concentrates containing chalcocite (Cu2S) and native copper using nonpyritic sulfur-bearing materials to aid matte formation. The procedure consisted of combining various proportions of commercial chalcocite concentrate, smelter slag, fluxes, and matte-forming constituents to produce charges of comparable compositions. The mixtures were charged in fire-clay crucibles and smelted in an induction furnace at 1,300° C. The research proved that either sulfur or gypsum can replace pyrite as a matte-forming material, and that gypsum produces an exceptionally high-grade copper matte. The addition of small quantities of metallic iron to the nonpyritic smelting charge furthers the removal of sulfur, improves the recovery of copper, and makes it possible to utilize gypsum as the exclusive flux and matte-forming ingredient, thereby eliminating the necessity of adding limestone.

Jan 1, 1968

By Stanford O. Grodd

The Sanford Lake district encompasses an area covering 24 square miles in the central Adirondack Mountains of northern New York State. Discovery of the titaniferous magnetite deposits dates back to 1826. Several attempts to exploit the ores for iron prior to 1942 proved uneconomical because of difficulties with the associated titanium, lack of transportation facilities, and the isolated location. Since 1942, the National Lead Company has produced ilmenite concentrates for the titanium pigment industry, and a magnetite by-product used in the steel and refractory industries. Rocks of the area are Precambrian in age and of igneous origin. The area has a history of erosion, deformation, and metamorphism, subsidence, and finally uplift and glaciation. The resulting topography is extremely rough with drainage patterns controlled by a combination of fault patterns and glacial modifications. The district is within the large anorthosite massif making up the central high peak area of the Adirondacks. All of the various lowsilica rock types associated with the massif are found within the boundaries of the district. These consist of both the Marcy and Whiteface types of anorthosite and of gabbroic anorthosite, gabbro, and different grades of titaniferous magnetite ores. All of the rocks contain the same minerals and differ only in their percentages of these consitituents. Gabbro, and ore associated with it, demonstrate flow structure as both have foliation and lineation. Anorthosite and its associated ores are massive and show very little primary structure. Minor pegmatites and diabase dikes provide evidence of remobilization in selected areas and of late intrusion as well. Faulting is prevalent and follows a regional pattern of major faults trending northeastsouthwest and of minor faults at nearly right angles to them. There are four mineralized areas where an economic grade of ore has been found. Three of these have both gabbroic-type ore and anorthositic-type ore. The fourth has only gabbroic ore. Ores are graded according to their TiO, content, and these range from 9.5 per cent to over 30.0 per cent TiO,. Ore bodies of both types are related to gabbro and conform to the configuration of the gabbro bodies within the anorthosite. At least three distinct theories of ore genesis have been expounded by different investigators. Others propose some variations of one or more of these. Although complete agreement probably never will be reached, it is certain that no one process of ore emplacement can explain the complicated picture as seen today. Further understanding of the ores and their origin will require detailed mapping, sampling, and mineralogical studies of the entire district, and then it may never be understood without qualification.

Jan 1, 1968

By C. W. Hoffman

A fairly recent development in the field of particle separation is now under investigation to determine its value to the mining industry. The method employed is probability sizing through a vibrating network of decreasing screen openings. While probability sizing as such is not new, the possibility of using it for coarse, highly abrasive ores at high tonnage rates has only recently appeared to merit practical consideration. The advantages to be gained by the use of probability sizing vs. conventional screening methods are: reduced space requirements for a high capacity unit, fewer moving parts, more versatile product sizing selection, reduced maintenance requirements and lower power consumption.

Jan 1, 1968

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By C. C. Koch, M. L. Picklesimer

PHYSICAL metallurgists interested in the alloying behavior and phase transformations in rare-earth metals and alloys require a strain-free polished and etched surface for both metallographic and X-ray examination. However, the rare earths have presented a problem in this respect since they are difficult to polish free from strain and are very reactive to the atmosphere. Their tendency to oxidize readily even at room temperature necessitates careful preparation and rather elaborate protection if their surface is to be examined for any length of time. The "light" lan-thanides (i .e., atomic numbers less than 63), especially lanthanum and cerium, are particularly bad in this regard; they oxidize very rapidly at room temperature. To eliminate the problem of plastic deformation remaining on the surface after mechanical polishing, electropolishingl and chemical polishing techniques2 have been developed. The electropolishing technique requires the specimen to be immersed in an electrolyte at -77°C and thus obviates a metallographic study of, for example, the fcc —double-hexagonal close-packed (dhcp) transformation in cerium which begins at -10°C. The chemical polishing solution has been used only on several of the "heavy" rare-earth metals. However, a convenient method for protecting the polished and etched surfaces from atmospheric corrosion has not been available. Our interest in the superconducting properties of lanthanum, and in the phase transformations in lanthanum and cerium, has led us to develop a technique for the metallographic preparation of lanthanum and cerium which clearly reveals the microstructure and preserves the etched surface for days. The specimens are chemically polished and anodized. The chemical polishing is performed at room temperature, the anodic oxide film provides the required protection from the atmosphere, and colors produced in the film provide a simple positive technique for phase identification. Lanthanum and cerium metal ingots obtained from Johnson Matthey and Co., Ltd., were remelted to suitable shapes and heat-treated to produce various microstructures. The samples were placed in epoxy mounts and, after a small hole was drilled in the back of the mount for electrical contact, were ground on silicon carbide

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By Ogden Tweto

The Leadville district, on the west flank of the Mosquito Range in central Colorado, has produced silver, zinc, lead, gold, and minor metals valued at $512,000,000. The ore deposits are in a sequence of dolomites and quartzites, Cambrian through Mississippian in age and about 500 feet thick, which is extensively intruded by porphyry sills, dikes, and plugs of Tertiary age. The sedimentary rocks and sills dip about 15°E and are broken by many faults, which are predominantly of nearnorth trend and downthrown to the west. The ore deposits are principally blanket or manto replacement deposits, but in the eastern part of the district many veins occur also. The replacement deposits are largely confined to three dolomite units in the stratigraphic sequence. Of these, the uppermost or Leadville Dolomite is the most productive. Most ore bodies are on the underside of porphyry sills and, particularly, beneath sills that occupy unconformities. Many replacement bodies have vein roots or branch from veins. The veins occupy faults and are productive mainly in the section of quartzites and dolomites and included sills. The primary ores consist principally of pyrite, marmatitic sphalerite, and galena but locally contain chalcopyrite, silver minerals, bismuth minerals, and gold. Principal gangue minerals are manganosiderite and jasperoid. The ore deposits have a crude zonal pattern centered around an intrusive center at Breece Hill, which evidently influenced ore deposition thermally. The ore deposits were oxidized to depths of several hundred feet in Miocene time. Bonanza ores mined in the early days were characterized by cerussite, cerargyrite, and embolite. Later, zinc carbonate ores were identified and mined on a large scale. The Leadville district is a complexly faulted and intruded area at the intersection of major fault systems trending N20°W and N15°E in the Mosquito Range. The intensely fractured area evidently localized igneous intrusion and subsequent mineralization. Ore solutions rose on many of the faults in the area, presumably from the same source as the porphyry magmas. Movement on these faults continued into the Pleistocene, displacing ore bodies, oxidation zones, Pliocene sediments, and glacial deposits.

Jan 1, 1968

By Frank G. Snyder

The Precambrian of Midcontinent United States includes a metamorphic belt of probable Middle Precambrian age, a belt of Keweenawan volcanics and sediments, and widespread igneous activity that extended from Iowa to Texas. Most of the present structural configuration of the Midcontinent was developed by epeirogenic movements during the Paleozoic. The dominant elements are basins and arches. Three major metallogenic provinces occur in the Midcontinent. They include the Missouri Precambrian iron ores, the Lake Superior copper ores, and the Mississippi Valley lead-zincbarite- fluorite deposits. Several large iron deposits, occurring in rhyolite and andesite host rocks, are known. Both discordant massive bodies and replacement- type bodies occur. The iron deposits are believed to have been formed during the period of igneous activity. They are essentially the same age as the volcanics and older than the granites that intrude the volcanics. The Lake Superior copper ores include two established districts, the Keweenawan district and White Pine, and the copper-nickel deposits in the Duluth gabbro. The lead-zinc-barite-fluorite deposits include four major districts, Southeast Missouri, Upper Mississippi Valley, Tri-State, and Illinois-Kentucky, and at least eight minor districts. Ore may occur in stratiform deposits and in veins. The major districts all contain stratiform deposits, but several have produced appreciable quantities of vein ore. Only vein deposits are known in some of the smaller districts. The major features of all districts can be catalogued in terms of host rocks, structural patterns of districts, types of ore-bearing structures, and mineralogical characteristics. From these features, a Mississippi Valley type ore body, in its type area, can be defined.

Jan 1, 1968

By M. C. Flemings, F. R. Mollard

Two-phase Pb-Sn alloys, ranging in compositiotz from 12 to 26 at. pct Pb, were unidirectionally solidified in a convection-fvee system, with thermal gradients in the liquid of up to 480°C per cm. Plane front solidification Loas achieved in all alloys at sufficiently steep gradient and slow growth rate. Conditions causing breakdown of the interface to a cellular or dendritic structure were roughly as predicted by a sinlple constitutional supercooling criterion. Structures of alloys of near-eutectic composition, solidified with plane front, exhibited a lamellar structure; the alloys furthest from the eutectic exhibited a rod-like morphology. Assumptions used in a previous paper for calculations of solute redistribution in two-phase plane front growth are shown to be reasonable for Pb-Sn alloys. Results of calculations are in good agveement with experiment. These show that variations in growth rate during solidification of the composite produce marked changes in average composition of the solid. IN a previous paper, Part I,&apos; conditions necessary for plane front solidification of two-phase alloys were discussed and calculations given on solute redistribution in this type of solidification. This paper, Part 11, describes experiments on Pb-Sn alloys, designed to check the assumptions of the analyses presented, and to demonstrate their applicability to a given alloy system (Pb-Sn). APPARATUS AND PROCEDURE General. A vertical crystal growing unit was built for the study as described below, and "normal solidification" employed throughout (i.e., the ingot was completely melted except for a portion near the bottom end and then solidification initiated). The furnace was designed to permit achieving very low interface velocities, and steep gradients, in essential absence of convection; it is sketched in Figs. 1 and 2. Simple heat flow considerations indicated choice of a small-diameter specimen (ingot) to achieve high thermal gradients; ingot size chosen was 0.3 cm in diam. The ingots were held inside silica tubes 0.06 cm wall thickness. The requirement for an essentially convection-free system was met by use of the vertical furnace with the heat source over the heat sink, as well as by use of the small diameter ingots. In addition, by selection of tin-rich Pb-Sn alloys, the diffusion boundary layer (lead-rich) was denser than the bulk liquid and would not cause convection. The only apparent driving force for convection in this system was the small transverse temperature gradient resulting from heat flow into the samples from the furnace. Such convection must have been small, however, since 1) no temperature fluctuations in the melt were noted in the recordings, which would have indicated turbulent convection, and 2) experimental results obtained and described below could not have been achieved in presence of significant convection. Ingot Preparation. Pb-Sn alloys ranging from 12 to 26 at. pct Pb were prepared from high-purity lead and tin (99.9999 pct pure metal). Each alloy was prepared by first melting the pure metals in the proper ratio in air, in a Pyrex container. The melt was then stirred thoroughly with a graphite rod and cast into a preheated graphite mold. Ingots were then prepared from these castings for use in the actual experiments; each ingot consisted of a rod of alloy, 15 cm long in a 25-cm-long transparent fused-silica tube, 0.3 cm ID and 0.06 cm wall thickness. One chromel-alumel thermocouple, made with 0.004-in.-diam wire and protected by a two-hole alumina tube, was inserted into each ingot. The 1.5 cm of the thermocouple nearest the bead were protruding from the alumina tube and were coated with a very thin layer of boron nitride paste which provided electrical insulation while allowing good heat conduction. The electrically welded junction size was about that of each wire and the cross section of the two wires represented about 0.3 pct of the sample cross section. Including the coating, the thermocouple cross section still represented less than 0.5 pct of the ingot cross

Jan 1, 1968

By R. Gibala

Internal-friction measurements on hydrogen-charged iron over the temperature range 4° to 300°K are reported. Two relaxation peaks, the hydrogen Snoek peak at 48 °K and the hydrogen cold-work peak in the range 145" to 2200K, are observed at 80 kc per sec. The effects of hydrogen-charging, aging, and deformation on the internal-friction results are determined and are used to show evidence of partitioning of hydrogen between solid solution and dislocations. The hydrogen-dislocation binding energy is estimated from the behaviors of the relaxation tiwzes and relaxation strengths of the Snoek peak and the cold-work peak. Its value is approxi,mately 6400 cal per mole. MANY investigators have demonstrated the usefulness of internal-friction measurements in determining the manner in which interstitial impurities interact with dislocations in bcc metals. Part of this success has resulted from the existence in bcc interstitial alloys of two anelastic relaxation peaks—the Snoek peak&apos; and the cold-work or Koster peak2 (designated hereafter by SP and CWP, respectively). The SP has its origin in the redistribution of interstitials in solid solution among sites made energetically nonequivalent by an applied stress. The rate at which the redistribution occurs, measured by the relaxation time for the process, is related in a simple way to the diffusion rate of the interstitial in the free solution. The relaxation strength is proportional to the concentration of interstitial in solid solution. The CWP appears to have its origin in the relaxation of an interstitial-dislocation complex for which the relaxation time at a given temperature is much longer than that for the SP. The relaxation strength depends strongly on the concentration of interstitial and the amount of deformation at relatively low concentrations and deformations.2-8 From the dependence of the relaxation strength on interstitial concentration, the SP and CWP may serve as measures of the concentrations of interstitials in free solution and bound at dislocations, respectively. Thus their behaviors have been used to investigate interstitial-dislocation interactions in Fe-C, Fe-N, and several refractory metal systems.&apos;-&apos; However, the Fe-H system has not been studied extensively,? even though disputes in recent years over the mechanism of hydrogen embrittlement in steels involve argument over the extent to which lattice hydrogen and hydrogen-dislocation interactions play an important role.?-&apos;&apos; Previous work on Fe-H indicates the internal-friction behavior to be qualitatively consistent with that for other systems. Apparently, both a SP and a CWP are observed in the temperature ranges 30" to 50°K and 100°to 140°K, respectively (at 1 cps). However, there is neither sufficient nor accurate enough information to identify convincingly these peaks with their supposed counterparts in other systems. Nor have there been any attempts to make quantitative use of these peaks to study hydrogen diffusion, aging, or interaction processes. In this paper, an attempt is made to obtain more complete information on internal friction of hydrogen in iron than presently available. Internal-friction measurements in the range 4° to 300°K on hydrogen-charged iron show that the two peaks discussed above are in fact the hydrogen SP and CWP. Several effects of hydrogen charging, aging, and deformation on these peaks are observed and are used to determine the partitioning of hydrogen between solid solution and dislocation sites in iron. EXPERIMENTAL Materials. The starting material for this investigation was a high-purity iron supplied by National Research Corp. as a 1-in.-diam rod. The following analysis was given (inwt pct): C, 0.004; N, 0.0003; 0, 0.007; P, 0.002; S, 0.005; Si, 0.006; Mn, 0.001; Cu, 0.002; Ni, 0.005; Cr, 0.001; Mo, 0.001. After an initial vacuum anneal (-5 XTorr) at 700°C, the rod was cold-

Jan 1, 1968

By Paul Gemmill

Production was first recorded from the Pioche district in 1864, and it has continued to show an inherent ability to take on new life after periods of depression in the metal markets. Production from replacement leadsilver- zinc sulfide ore bodies in limestones of Cambrian age now accounts for several times the gross value of silver production from rich fissures in Lower Cambrian Quartzite. Aggregate production of some 6 million tons represents a gross value over $100-million. Future output is expected mostly to be from limestone replacement deposits of which the most productive are "channels" of ore up to several hundred feet wide and several thousand feet long with thicknesses from a few feet up to 50 feet. Such channels are restricted to the lowermost limestone bed of the district, about 250 feet above the basement quartzite. The "blotter-like" characteristic of this highly productive Jimesto~e bed in absorbing mineralization is believed to be, at least in part, due to lithology, including free carbon in the bed, which has created a unique set of conditions for delicately balanced mineralizing solutions that rejected any tendency to replace siliceous wall rock and were properly constituted for replacement of Limestone. All recognizable orogenic history is considered to be related to the Basin and Range faulting that created the mountain ranges. The faults developed after mid-Tertiary time and after widespread extrusives that are themselves involved in the faulting. Flat faults, formerly believed to be part of regional thrust faulting, are now interpreted as gravity slide faulting that can be shown to be large in magnitude and not simply local landslides. Large slide faults generally have concealed the great magnitude of mountain-bordering faults. Mineralization that accounts for ore is later than the faulting. Most faults are pre-mineral since they influence the shape of ore bodies, and some clearly have been offset by fault fissures containing ore. Post-mineral movement probably has been an important component of some large, initially pre-mineral faults. A single period of mineralization was begun by the introduction of large quantities of ironmanganese carbonate, and, in places, carbonate manganese with minor values in sulfides. Closely following the carbonate invasion, massive sulfides were brought in, usually replacing part of the carbonate body though in some places the massive sulfides replaced limestone that was not previously mineralized. Manganese mineralization is not a "halo" but leaks of manganese to higher formations and to the surface are the most significant exploration guides. The Pioche district is expected to be long lived with technological developments in ore treatment being important to the exploitation of low-grade manganiferous ores, while aggressive exploration is expected to find important quantities of bedded lead-silver-zinc ores of the massive sulfide type.

Jan 1, 1968

By Kenneth Blower

This paper gives a detailed coverage of the ore flow through the primary crusher, cobbing plant and concentrator, including equipment sizes, recoveries, reagent consumptions and product descriptions. Special features, such as rubber chutes, rubber-lined mills, pebble-mill grinding, steam-hooded filters and process control instrumentation, are also discussed.

Jan 1, 1968

By John F. Elliott, John P. Hager

The standard free energies of formation of the lowest stable sulfides of chromium, molybdenum, and tungsten in equilibrium with the corresponding metal hazle been determined by reacting the sulfide and metal with H2(g)/H2S(g) mixtures. The reaction is A method for estimating the standard ~nolav entropies and standard entropies of formation at 298°K of the sul-fides of refractory metals is presented. The standard free energies of formation of the lowest sulfides of the metals in group VIa of the periodic table are probably best determined with the reaction* is known with greater accuracy than is that property for any other sulfur-bearing compound or solution which might serve as a reference phase to establish the chemical potential of sulfur for the essential re- However, there still remain significant problems to the use of Reaction [I] in studying these sulfides. First, the equilibrium gas ratios (Ph2S/PH2) are very small, and with the most stable sulfides in the series the ratios tend to be at the limit of the range for precise chemical analysis (10-4); and second, the reaction rate for the formation or reduction of these sulfides appears to be relatively slow. A primary reason for the latter problem is that the gas phase near the equilibrium concentration has very little capacity for transport of sulfur. It is to be noted that the thermo-dynamic properties obtained from the experimental results by Eq. [I] apply for 1 g-atom of sulfur in the metal-saturated compound even though the exact composition of the compound has not been determined. The work reported here is a study of the standard free energies of formation of the lowest sulfides of chromium, molybdenum, and tungsten, and of copper, by Reaction [I]. In planning the experimental program, it was decided that the technique that has been used previously3"&apos; could be used with modification and that an improved analytical method was needed for determining H2S in the gas phase. THE EXPERIMENT The once-through flow of gas was selected in preference to recirculating the gas, a) because of the low sulfur capacity of the gas, b) because of the relatively slow rate of reaction and the danger of the

Jan 1, 1968

By D. W. McGlashan

[Becaune ad ;the extennive nwrgace anea od u.X chopRex2 in emmiom, emuhion dRokdtiun oddeh poaaibWa don ;the necove/ry ul; BinQey divided minmcd pa~LL&a, Swr~aC;tavu% mu2 akab&ze ;the emu-bion and poan an an ad~i&y don ;the dahed mina&. OZhm hpohtant acto oh me ;the naAwre od ;the em&iun inghedied, ;the nQRaLLve volwna 06 the colz;tinuoun and dincon;tinuoun phaa, ;the change aign bonne by the dnuplm ad the o.X phae, ;the z&a pu;tenticd od ;the dahed minmd, the ~olubRe am curdent 06 khe wcr;ten-pulped and gnuund onu. AX on nem ;the AoQRec;trtic point on ZPC, ;the doubRe Raym about ;the minW-&den oil dnopR& i~ neduced in ;tkichnaa and the dn_opR& wU codace and continue to aggnegate into agglommaka . Invetmion dnom O/U ko W/O can UCCWL depending upon a nwnbm a 6 in;tmQeaked daotuh~. EReothokin&Lc inn&wnenta;t/iun to meanwre ;the ZPC, QReckProphonQkic mobilXty z&a pokeW and hakerning cuttrtent me invcduabte in ;the appficatiun ud emu-bion dRo;tat;iun ;to m&~c and nonm&~c minu.&. ] INTRODUCTION Recent interest in emulsion flotation can be ascribed to the necessity of selective separation and concentration of extremely fine minerals. That which follows is an elucidation of the many factors-in emulsion technology in application. In applied surface chemistry for solid-particulate separation and concentration, emulsion flotation is one of the intermediate processes between froth flotation, in which the continuous phase is water (99.5 to 99.999% by volume), and particulate extraction, in which the continuous phase is almost entirely an organic-fluid. Another intermediate process is particulate exchange (or partition) in which immiscible or very limitedly miscible phases are in controll¬ed but appreciable volumes. Surfactants are common to all of these

Jan 1, 1968

By Culver, Richard S.

In spite of the widespread interest in rock bolt research, relatively little is known about the critical region surrounding the bolt anchor. In analyzing the stress distribution around an opening resulting from rock bolt support, it is commonly assumed that the bolt is fixed at a point far enough from the surface so that the anchor does not influence the performance of the bolt. Furthermore, a bolt anchor is assumed to per- form satisfactorily if it will hold the design load with a minimum amount of load relaxation, commonly called bleedoff. From the standpoint of the design engineer both of these assumptions are reasonable, but they ignore the fact that the extremely high stresses in the region of the anchor are capable of generating fractures in the rock. Lang estimated the bearing stresses for a slot and wedge anchor on a one-inch-diameter bolt to be as high as 125,000 psi. This paper describes a more thorough analysis of the magnitude of the stresses around the anchor and the nature of the potential fractures that might result.

Jan 1, 1968

By A. J. Strauss

The solubilily of lead in PbS as a funclion of lemperature has been investigated by means of Hall coej&apos;icient (RH) measurentents OIL samples prepared by annealing and quenching Bridgman-grourz single crystals, which contain excess lead incorporated during /heir growth from the mell. For sufficiently long annealing times and sufficiently rapid quench rules, the samples obtained consist of n-lybe PbS snturated with In the semiconducting compounds PbS, PbSe, and PbTe, the point defects associated with the presence of lead in excess of the stoichio metric composition are shallow donors. The defects associated with the presence of excess nonmetal are shallow acceptors. lead at the annealing teuiperatiire, together luilh a dispersed second phase of lead microprecipitates. Due to the retrograde solubility of lead, the measured free carrier concentration (n = l/eR77) decreases with decreasing annealing tewperature (T) from- 2.4 X 10 em-3 for 1l85OK to 1.3 X 1018 cm-3 for 623°K. The dala are well-represented by the equation n =(1.08 x 102) exp[ - (0.37 ev.)/kT] cm-3 For most undoped samples of these compounds, the carrier concentration at room temperature and below is determined primarily by the stoichiometry, since the concentration of either excess lead or excess non-metal is large compared to the concentrations of intrinsic carriers and electrically active impurities. Therefore the dependence of composition in temperature and partial pressure can be investigated by means of Hall coefficient measurements, even though the deviations from stoichiometry do not exceed 0.03 at. Pct

Jan 1, 1968

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968