Search Documents

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 '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'-4 or thermogravimetric measurements. 5,8 Darken and Gurry'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's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' 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.' 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' 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 Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg' have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck' established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

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 D. F. Malott

The Michigan Department of State Highways makes extensive use of geophysics for subsurface surveying which would be applicable for uses in other fields. Examples of resistivity surveys are given which include a proposed large volume excavation with suggestions for land use after excavation, subsurface evaluation for engineering design, and a subsurface survey for land appraisal. An example of a combined refraction seismic and resistivity survey is shown where the resistivity is used for outlining the unconsolidated soils, while the seismic method Is used to outline bedrock and to evaluate it for rippability. A refraction seismic survey at the bottom of bridge caissons for evaluation of bedrock uniformity and a relative aid In assessing rock strength is reported.

Jan 1, 1968

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By N. A. D. Parlee, E. M. Sacris

OXYGEN solubility in liquid silver has been well studied.1-6 It has been established that the solubility follows Sieverts' law reasonably well5'6 up to po2

Jan 1, 1968

By H. E. Powell, A. A. Cochran, R. E. Coleman

Infrared spectroscopy, employing the internal reflection method in conjunction with solvent extraction techniques, was used to study surface reactions between aqueous potassium ethyl xanthate and both sphalerite and precipitated zinc sulfide, each activated with aqueous copper sulfate. It was determined that reactions occurring on the sphalerite and zinc sulfide surfaces produce the reaction products ethyl dixanthogen and cuprous ethyl xanthate, some of which are adsorbed on the mineral surfaces. As the pH of the xanthate solution increased from 5.6 to 11.0, the amount of cuprous ethyl xanthate on powdered sphalerite surfaces decreased and the amount of ethyl dixanthogen first increased and then decreased. It is generally accepted that the collector potassium ethyl xanthate will not float the mineral sphalerite (ZnS). However, Gaudin1 showed that sphalerite readily floats if activated with certain metal cations before exposure to the xanthate. Copper sulfate (CuSO4) was found to be the best activator for sphalerite. The over-all flotation reagent reaction, as given by Gaudin,3 is as follows: While this is the over-all reaction, the exact mechanism of the reaction and the intermediate compounds that may be formed are not yet known with certainty. Important work has been done in Russia by Plaksin

Jan 1, 1968

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

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,' 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 S. S. Lau

The authors of the previous comment stated that Dorn and Rajnak33 and others34-40 concluded that "agreement with this function [(t'/tp) -f(Un/2Un) = T/Tc} may be used as a criterion for that (the Peierls) mechanism of deformation". In contrast, however, Dorn and Rajnak33 and others34-40 never made such a statement. In order to clarify the issues involved it is appropriate to recapitulate the conditions that must be satisfied in order to suggest that some deformation process might obey the Peierls mechanism: 1) Within permissible variations due to changes in the slope of the Peierls hill the T*/Tp - T/Tc relationship must be obeyed. Although some mechanisms, e.g.. solute atom stress field, recombination of dissociated partials in bcc metals, intersection of dissociated dislocations, and so forth, give about the same t* - T relationship, other mechanisms, such as cross slip, disruption of attractive junctions, climb, motion of jogged screw dislocations, and so forth, give distinctly different t*-T relationships. On this basis some distinction can be made of the various mechanisms. 2) An important feature of the Peierls mechanism concerns its physical origin based on the nucleation of pairs of kinks. The value of T* at 0°K increases with the density of dislocation (i.e. , cold work) for the intersection mechanism and it increases with the square root of the atomic fraction of solute atoms in the solute atom interaction mechanism. In contrast the value of t* at 0°k, for the Peierls mechanism which depends only on the line energy and the shape of the Peierls hills. is independent of cold working and the square root of the solute atom concentration. These differences have been employed by various investigators for elimination of a few other possible mechanisms. On the other hand it is not possible to eliminate all mechanisms, e.g., the recombination of dissociated dislocations in bcc metals, and so forth, on this basis alone. 3) Further discrimination between possible mechanisms is based on the activation volume. For the in-

Jan 1, 1968

The problems of using comparatively simple x-ray diffraction equipment for quantitative analysis are examined. Internal standard and direct calibration procedures based upon the measurement of integrated diffraction energy (diffractometer peak area) have been developed for the determination of quartz in Broken Hill dusts. By these methods an accuracy of ± 10 per cent of the true value can be obtained and this can be improved to ±2 1/2 per cent by statistical methods if necessary.Rapid analysis for the components quartz, muscovite, rhodonite, galena, fluorite, sphalerite, calcite, and garnet has been developed by adaptation of direct calibration procedures and use of maximum diffraction energies (diffractometer peak height). Until more is know!) about the pathological effects of multi-component dusts of the Broken Hill type it seems undesirable to fix theIr allowable concentrations in terms of the quartz content.

Jan 1, 1968

By J. Gurland, A. Gangulee

The cracking of silicon particles embedded in an aluminum matrix occurs progressively over the range of plastic deformation of the composite specimen. The fracture probability of the particles increases with increasing particle size and decreasing silicon contents. The crack orientation tends to be perpendiculay to the direction of the maximum tellsile strain. An example of a direct association between matrix slip and particle cracking is shorn. ALUMINUM-SILICON alloys of commercial compositions fail by ductile fracture in three stages:' I) initiation of cracks in the silicon particles, 2) growth of cracks into cavities, and 3) rupture of the aluminum matrix separating the cavities. The present work is concerned with the first stage: the initiation of cracks in the silicon particles. EXPERIMENTAL PROCEDURE Aluminum samples with 2.8, 6.1, 9.6, and 13.2 vol pet Si, respectively, were cast from commercial al- loys. Machined tensile specimens (2 in. gage length) were annealed in air at 1000°F for 100 hr, and then pulled at a strain rate of 0.025 per min. The grain size (average linear intercept) of the aluminum matrix was 0.24 and 1.6 mm in the 6.1 and 13.2 pet Si alloys, respectively. The particle size of silicon in alloys of one composition (6.1 pet Si) was varied by either modifying the castings with 0.15 pet Na or prolonging the annealing time. The average particle size was measured by linear and planar analysis, assuming spherical particles of uniform size. The particle sizes and compositions of all samples are tabulated in Fig. 8, together with the identifying symbols used in the graphs. The respective numbers of broken and unbroken silicon particles were determined from metallographically prepared longitudinal sections by counting a total of approximately 2000 particles per sample. EXPERIMENTAL RESULTS 1) Crack Initiation During Deformation as Function of Composition. Nominal stress-strain curves of four specimens of different compositions, but approximately equal particle sizes, are presented in Fig. 1. The fraction of broken particles, P (no. of broken particles/ total no. of particles), is shown in Fig. 2 as function of true stress and in Fig. 3 as function of nominal strain. The last point of each composition line in Fig. 2 rep-

Jan 1, 1968

By L. B. Pankratz

The Bureau of Mines conducted heat-content measurements above 298.15° K for dehydrated analcite (NaAISi2O6) to 1,000°K, kaliophilite (KA1Si04) to 1,800° K, and leucite (KAlSi206) to 1,800° K. Heat content and entropy increments were tabulated, and the heat content data, were given in equation form. A first order transition was noted for kaliophilite near 810° K with a heat absorption of 160 cal/mole. Leucite had a second order transition which became complete near 955° K. In this transition a crystal change occurred from tetragonal (low-temperature form) to cubic (high-temperature form).

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' 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.'-' 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.?-'' 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"' 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 T. J. Neil, C. B. Manula, O&apos

This paper describes a simulation model developed to analyze truck haulage problems as they are found in the open pit mining and construction industries. The model, using a computer, cycles trucks between their assigned loading and discharge points over a measured haulage route. Required parameters for model operation include the number and type of operating trucks and loading units, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each origin. Equipment performance characteristics, system profile characteristics, and service time distributions are also included. Records are kept of all waiting times at the loading and discharge points and of any truck interference on the haulroads (moving queues), and a current journal of ore and waste production is maintained. In the pursuit of reduced truck haulage costs, management is confronted with three particular problems in truck and shovel mines. 1) What is the best assignment of trucks to shovels in the system? 2) If new equipment is needed, which new shovels and trucks will operate most effectively in the system? 3) Are any physical changes in the haulage layout warranted to increase productivity? For small open-pit mines the answers to these questions may be obvious. However, for larger operations complex problems are encountered with production and system configuration relationships usually being unknown. The mining simulator discussed here was developed to aid management in evaluating alternative pit-haulage schemes to reduce the risk involved in the selection and assignment of equipment in open-pit truck and shovel mining systems. There are two fundamental differences between this model and other truck haulage simulators: one is a difference of degree, the other a difference of kind. This model can simulate more complex systems than previous models by allowing transportation of material from multiple mine faces to multiple mine destinations and by being readily adaptable to a wide variety of mine layouts. The second difference that characterizes the model is the standard simulation of truck movements. This technique enables each vehicle to perform according to its mechanical capabilities and the physical profile of the haul road. Among the similarities between other truck haulage simulators and this model are the recognition of the probabilistic nature of certain service times in the system and the use of a digital computer to operate the model. The computer inherits the staggering computational and bookkeeping work loads and provides a means for compressing the time scale by allowing several days' operations to be simulated in a matter of minutes. DISTRIBUTION SYSTEM Basic aspects of the system analyzed here may be brought into focus by referring to Fig. 1, a schematic of the typical open pit truck-shovel operation programmed into the simulation model. A single stage materials handling scheme is employed to transport both ore and waste. Loaded trucks are directed to a crusher or stockpile if ore is being mined, while overburden is conveyed to a waste dump. Each shovel has a given number of assigned trucks and has two associated haulage routes, one for waste and one for ore. Up to 5 shovels and as many as 10 trucks per shovel (or a total of 50 trucks) can be operated in the model. Essentially the model, using a computer, cycles trucks between their assigned shovels and the proper discharge points over measured haulage routes. Required input parameters for model operation include the number of shifts to be simulated, operating time per shift, number and type of operating trucks and shovels, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each shovel. Equipment performance characteristics, system profile characteristics, and service time distributions are

Jan 1, 1968

By A. Hansson, G. E. Tardiff

WHILE it is generally known that cold-worked low-and medium-carbon steels exhibit substantial increases in tensile rupture ductility with increased deformation velocity172 (up to the von Karman limit), the observations for annealed or normalized steel do not permit simple generalization. Various investigators, for example, have reported both small increases1,3 and small decreases4,5' in rupture ductility with increased rates of deformation of normalized low-carbon steel. The purpose of the present note is to report on the dependence observed for strain-aged steel since preliminary work here indicates that strain aging results in the development of a consistent type of behavior that is understandable in the light of current knowledge of the lower yield dynamics for steels which deform inhomogeneously.6 This realization throws additional light on the influences responsible for the behavior of normalized steel. The results presented here were obtained for a 0.21 pct C, 0.012 pct N sheet (0.012 in. thick) steel which was received in a temper-rolled condition (approximately 3 pct reduction in thickness after process annealing); the as-received material had a spherodized structure with a ferritic grain size of ASTM 8. The material was selected for testing after 6 months room temperature aging, at which time the static lower yield and ultimate tensile strength measured 79 and 82 kpsi, respectively. ASTM 2-in. reduced section, 1/2-in.-wide specimens were used in smooth bar tests and 3/4-in.-wide specimens containing two 60-deg opposed edge notches (root radii = 0.002 in.) were used in notched bar tests. To facilitate strain measurement, the smooth bars were blued with ink and marked at 0.1-in. intervals along the gage length; the notched

Jan 1, 1968