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By L. M. Cathles, H. R. Spedden, E. E. Malouf

Fluid flow through an igneous rock formation will occur mainly through fractures. A non-diffusing or slowly diffusing tracer (such as .5µ silica spheres identifiable under electron microscope) will arrive at a monitor well when enough fluid has been injected to displace the volume of water in the flow fractures between the injection and monitor wells. A rapidly diffusing tracer (such as NaC1)-will diffuse into the matrix blocks and so a volume of tracer nearly equal to the total fluid volume contained in the rock formation between injection and monitor wells must be injected before significant diffusing tracer arrival will be noted. The flow fracture porosity is typically one hundred times smaller than the total porosity of an igneous formation. The shift between diffusing and non diffusing tracer arrivals, together with the diffusional characteristics of the tracers, can define the diffusional accessibility of the matrix blocks of an igneous formation. A field test of these concepts and the problems encountered will be described.

Jan 1, 1974

By J. L. Huiatt, D. G. Foot

The Bureau of Mines devised a direct flotation method for treating low-grade carnallite (KCl*MgC12*6H20) and sylvinite (a mixture of KC1 and NaCl) ores characterized by a high content of water-insoluble impurities. The procedure consists of flocculation-depression of the insoluble slimes; decomposition leach (carnallite only); potash rougher, cleaner, and recleaner flotation; and final product leaching. The technique eliminates the necessity of removing the water-insoluble slimes by mechanical or flotation desliming. Laboratory results demonstrated that the direct flotation procedure, when compared with conventional techniques, yielded equivalent or improved flotation results with equal or less reagent consumptions. The direct flotation method recovered 81.6% of the solid phase KC1 from camallite ore and 79.7% of the KCl from sylvinite ore in final products containing 60.5 and 60.9% K2O, respectively. A flowsheet incorporating the described flotation procedure is presented.

Jan 1, 1983

By W. P. Sykes

TUNGSTEN serves mankind in two major roles. The first of these is represented by the tungsten filament of the incandescent electric lamp, a common article of commerce. In the field of hard alloys it plays its second substantial part. A fortunate combination of physical properties in this metal ac- counts for its efficient service as a source of illumination. Tungsten melts at about 3400°C, has a relatively low vapor pressure and at the same time sufficient strength, both hot and cold, to serve satisfactorily as filaments, which may range in diameter from 0.060 to 0.0005 in. In the early days of the incandescent lamp, the pioneers realized the importance of using a substance of high melting point for the source of light. The metals osmium (mp approx. 2700°C) and tantalum (mp approx. 2850°C) were both employed to some extent. Tantalum actually attained some commercial importance in this field because it could be drawn into small wires of appreciable length. DUCTILE TUNGSTEN WIRE Before the year 1908, tungsten was considered a nonductile metal, since no one had succeeded in overcoming the brittleness so typical of the unworked metal at room temperature. The methods employed today in producing ductile tungsten wire were developed over a period of years. The process was largely determined by the exceedingly high temperature required to melt this metal. Even today the difficulties involved in producing an appreciable quantity of pure

Jan 1, 1953

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m''ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By C. M. Brinckerhoff

Safety work in mining at the Andes Copper Mining Company, Potrerillos, Chile, is divided into three parts: (1) accident prevention, (2) fire prevention and protection, and (3) silicosis prevention and control. In the company's operations a steady campaign has been waged to reduce accidents and silicosis, and to prevent fires. In the following pages the safety record for the past twelve years will be examined and the methods explained by which the accident rate was reduced. Table 1 contains yearly data pertaining to the scale of the mining operations and the accident record. Block caving is used for all ore production and the tonnage mined has averaged 30,000 short tons per day for the past seven years. Table 2 classifies 44 fatal accidents which have occurred since 1935. The leading causes of accidental death are transportation of ore and use of explosives, followed in order by persons falling, falls of ground, and by asphyxiation. In the case of serious accidents, however, the greatest cause is falls of ground, followed, in turn, by ore transportation, persons falling, explosives, and asphyxiation. Accident Prevention The improvement of the safety record was obtained by a combination of many factors. In surveying the results at Andes for the past twelve years, it is possible to select some features of the present operation which have contributed to the accident record. The most important of these are: (1) good staff planning, (2) good equipment, (3) an alert safety organization, and (4) education and selection of the workmen. GOOD STAFF PLANNING As a result of good staff planning, the mine has good working conditions, namely, good ventilation, moderate temperatures and humidity, and good lighting. These factors not only reduce accidents but also improve efficiency. In haulage work, accidents have been reduced by having traffic move in a forward direction only. The latter makes possible a one-man train crew. Trains are centrally dispatched from loading drifts which are interconnected by signal lights, so that when a train in a lateral drift is given permission to move into a main line drift, a red light signals in all other lateral drifts in that area. Good track is maintained, and safety niches are required at all switch throws. Since safety niches were provided there have been no fatal or serious accidents at such points. All main line haulage drifts are illuminated by electric lights. Haulage drifts are kept clean. Adequate clearance has been provided between cars and between cars and the sides of the haulage drifts. The 4 1/2 ton Cranby type cars are equipped with roller bearings, and the 10 ton loconlotives with trolley shoes instead of wheels. These two features are responsible for improved ore haulage conditions and contribute to greater efficiency and safety.

Jan 1, 1950

By E. C. Bain

THE more familiar compositions of iron-carbon-chromium1 and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallographic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

Jan 1, 1899

By EDWARHD HALSE

Discussion of the Paper of Dr. H. M. Chance, presented at the Lake Superior Meeting, September, 1904. EDWARD HALSE, Puerto Berrio, Colombia, So. Amer. (communication to the Secretary*) : The Taviche mining-district is generally known as a Taviches," being named from the two villages called respectively San Pedro Taviche and San Jeronimo Taviche. It is so called by José G. Aguilera, in his paper on the Geographical and Geological Distribution of the Mineral Deposits of Mexico;' and in published reports by the late N. W. Rudston Read ;2 and by Juan de Dios Villarello.3 The region is a large one, measuring about 24 miles long and 7 miles wide. Dr. Chance, in his interesting paper, tells us very little about the nature of the ores, and, with regard to the geology of the district, contents himself with observing that ? the country, as a rule, consists of eruptive rocks; and no evidences of sedimentary strata appear near the mines.? The latter part of the above statement is hardly correct. The formation is mainly eruptive, being hornblende-audesite of Tertiary age, which is limited on the east by the calcareous (Cretaceous) formation, and on the west by the Huronian rocks of Ocotlan. Limestone is seen close to the Santa Càtarina mine, at the northern end of the region. In the surface-working known as La Cueva, a little northeast of San Pedro, limestone forms the eastern wall of the deposit which consists of spots (moscas) of pyrargyrite in white opaque or transparent quartz. Ill one place the ore is associated with stibnite, and the quartz frequently exhibts a

Sep 1, 1905

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By Subhas G. Malghan

Feldspathic deposits occur widely throughout the United States, but North Carolina, California, Connecticut, and South Carolina accounted for over 80% of the total domestic feldspar output for the year 1973.1 Pegmatites and granites constitute the major feldspar reserves of the United States, 2 and in addition, feldspar is produced as a byproduct by firms whose major products are spodumene and mica. 3 Feldspar flotation is practiced in the United States, Mexico, Finland, Norway, West Germany, Japan, and the USSR. According to the US Bureau of Mines estimates, the production of feldspar in the United States and rest of the world were 704,000 and 2,514,000 t, respectively. Feldspar is principally used as a flux in making glass, pottery, porcelain, enamel, tile, and other ceramic products. In recent years, the domestic feldspar industry is faced with a number of problems. As a result of increased cost of energy and the introduction in 1972 of new legislative programs relating to air, water, and noise pollution, land-use restrictions, and mined-land rehabilitation, the production costs have increased. Apart from the increased cost of operation, an operational problem exists with the feldspar producers in North Carolina, especially those in the Spruce Pine area. This problem is concerned with the use of hydrofluoric acid in the feldspar flotation. Feldspar producers in Spruce Pine, NC, have been discharging process waste water into the North Toe River. The mill waste water contains active fluoride ions. Fluoride in excessive concentrations is undesirable in waters used for drinking. It is stated that water containing 0.9-1.0 ppm fluoride will seldom cause mottled enamel on children's teeth; and for adults, concentrations less than 3-4 are not likely to cause endemic cumulative fluorosis and skeletal effect. Although the literature on this subject is rather confusing and inconclusive, the inference that concentrations over 4 ppm may affect bone structure is clear. According to the recent Federal Register,4 maximum fluoride level of 1.4 ppm at 79°-98°F is considered to be adequate and safe for the protection of health of the consumers. The EPA and state environmental agencies have accelerated their drive to reduce water pollution on a faster schedule. By 1977, the EPA specifications for maximum contaminant level of fluoride ions in the discharge waters of feldspar milling operatins is expected to be reduced to 2.0 ppm. The other problems of using hydrofluoric acid are the following: toxicity, hazards of handling and storage, and high cost as compared to other inorganic acids (almost 16 times the cost of sulfuric acid). In order to reduce fluoride levels in mill discharge waters, mining companies have taken the following steps: I) Recirculating a part of their mill water. Even though recirculation of mill water seems to be a novel method of reducing fluoride contamination of the discharge water, there are certain operational and handling problems. 2) Conducting research on the treatment of fluorides in mill waste water. The technology of treatment of fluoride ions has received considerable interest in the recent years. A recent research report5 estimates that the cost of fluoride ion removal to meet the present specifications in the feldspar industry is approximately $0.25/t of ore processed, and about $0.50/t of feldspar produced. At the request of the feldspar producing industries in North Carolina, the North Carolina State University (NCSU) Minerals Research Laboratory has taken up a research program directed towards overcoming the fluoride ion pollution problem. After a close study of the operational, technical, and economic aspects of feldspar flotation, it was decided to attempt to replace the conventional hydrofluoric acid process. Conventional Feldspar Flotatin Using Hydrofluoric Acid Since the inception of the feldspar flotation process using hydrofluoric acid by O'Meara2,6 the process has achieved a great commercial success. In the conventional flotation separation of feldspar-quartz, hydrofluoric acid is used to suppress quartz and activate feldspar, and a long chain amine salt (acetate or chloride) is used as a collector. The bulk of amine collectors used in current feldspar operations are applied as the water-soluble acetates of the free-base amines. These products are pastes or waxy solids which are available in a range of acetic acid neutralization levels generally 50 to 100% neutralized. In spite of the problems mentioned in connection with the use of hydrofluoric acid, this process is extremely stable with respect to changes in the process variables. With the exception of a few operations, alaskite and pegmatite are the major sources of feldspar.7 In the flotation treatment of a pegmatite that contains iron-bearing minerals (heavy minerals), mica, feldspar, and silica, a logical order of removal presents itself considering the following:8 1) Mica is readily floated by an amine collector in a pulp pH 3.5. Some iron-bearing minerals will usually respond to amine collector in acid circuit with the mica concentrate. 2) Since iron minerals tend to occur invariably in the feldspar concentrate, it is desirable to remove most of these prior to feldspar flotation. A fatty acid or a petroleum sulfonate collector used in this flotation step in acid circuit will float iron-bearing minerals. 3) Using hydrofluoric acid to maintain pH of 2.5, an amine collector employed in a final step will float feldspar away from silica, usually leaving the latter in the tailing as a high-grade silica concentrate. The problems connected with the flotation separation of feldspar-quartz arise due to the similarities in their chemical structure. Therefore, any reagent system that is likely to succeed in feldspar-quartz separation should have adsorption affinity towards one of the minerals and depression effect towards the other mineral.

Jan 1, 1979

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By A. E. Dwight, Paul A. Beck

Known CsCl-type phases in transition metal alloys are shown to be formed preferentially at an electron concentration of approximately 6; a tetragonally distorted version of the CsCl structure is stable at -e/a = 6.5. The relationship of the distortion to electron concentration is verified by experimental data for the quasibinary systems Time ,Os) , Ti(Re,Ir), and Ti(Re,Pt) and the ternary system Ti-Ru-Rh. It was noted some years ago1j2 that the occurrence of CsC1-type ordered structures in equiatomic binary alloys, AB, of transition metals correlates with the location of the component elements in the periodic table. One of the components, A, must be to the left and the other component. B, must be to the right of the chromium group. It was pointed out2 that the CsCl structure does not occur in CrFe. is metastable in VFe,3 and is stable in TiFe up to high temperatures, and that this progressively increasing stability may correspond to an increase in electron transfer between the two components and to a correlated decrease of the magnetic moment associated with the iron atoms. Such a decrease was in fact later demonstrated by Nevitt. 4 The binary CsC1-type phases that are formed by a transition metal with either another transition metal or a lanthanide are listed in Table I. Thirty-three of these phases occur at an average electron concentration (average number of electrons outside of closed shells) of e/a = 6. The five phases that are formed at an electron concentration of e/a = 5.5 appear to be borderline cases. This is suggested for instance by the fact that TiRe is bcc. without any long-range order, while TiTc (at the same electron concentration) has a CsCl ordered structure. Six of the undistorted CsCl phases formed by transition metals with one another have an average electron concentration of e/a = 6. 5. Table I. With the exception of Zr4,Rhs4 and Hf48Rh52. the B component in these phases is a first long-period transition metal, i.e.. iron or cobalt. TiNi. with an electron concentration of e/n = 7, appears to undergo transformation at around room temperature to a more complex ordered struct~re.~ The five other CsCl structures known to occur at e/a = 6.5 have either scandium or a lanthanide metal as the A component; the difference in the elec-tronegativity and in the e/a ratio between the component elements is in these phases very large, A(e/a) - 7, and they may be expected to have a rather strong ionic bond component. Presumably the ionic bond stabilizes the CsCl-type structure at the equiatomic composition and it overrides the electron concentration requirement. When the B element is not from the first long period and the A component is not a rare earth metal. equiatomic (AB) alloys of transition metals with an average electron concentration of e/a = 6.5 in most cases have a crystal structure closely related to the CsC1-type, but slightly distorted tetragonally, Table I. This was first found6 for VRu, NbRu. and TaRu. It was noted6 that the undistorted CsCl structure is also stable in the three systems. but at a lower electron concentration, near e/a = 6. In these systems this requires a deviation from equiatomic stoichiometry. which is otherwise ideally suited for the CsC1-type structure. A similar situation was later found in the Ti-Rh7 and the Ti-Ir systems. 8 The Ti-Rh alloys undergo a second distortion and become orthorhombic when the rhodium content becomes somewhat larger than 50 pct. As mentioned previously. TiRe does not have the CsC1-type ordered structure. In order to investigate how close TiRe is to the borderline of stability of the

Jan 1, 1970

By W. F. Hosford, E. W. Kelley

Deformation studies have been conducted at room temperature on single crystals of magnesium and magnesium alloys with thorium and with lithium. Single crystals oriented to suppress shear on the easily activated basal slip systems were deformed by plane-strain compression. Compression along the C axis was accommodated by {1011} banding. Compression perpendicular to the unconstrained c axis activated {1012} twinning, and, after virtually complete twinning, deformation continued by {1011) banding in the twinned material. Compression perpendicular to the constrained c axis was accommodated by the simultaneous operation of (1012) twinning against the constraint and (1011 ) banding. Although this orientation was favorable for {1010)(1210) prism and {1011}(1~10) pyramidal slip, these modes were not observed in pure magnesium or in Mg-0.5 pct Th. However, {10i0)(1~10) prism slip was observed in crystals of Mg-4 pct Li during compression perpendicular to the constrained c axis. Fracture in all materials occurred parallel to (1124) or {l~il) depending on the orientation and composition of the specimen. THE mechanical behavior of the hcp metals is strongly anisotropic. Although several slip systems have been reported the slip is cpmmonly in the directions of closest packing, the (1210),' and this does not produce strains parallel to the c axis. Hence the inherent anisotropy. The deformation mode most easily activated in magnesium at room temperature is (0001)(1210)- basal slip. Also {1010}(1~10) prism slip and {1011)(1210) pyramidal slip have been reported, primarily at elevated temperatures.2"4 However, at room temperature the shear stresses to activate the prism and pyramidal modes are roughly a hundredfold greater than that required for basal slip.'j4 Thus prism and pyramidal slip may be expected only under special conditions of loading. Strains normal to the basal plane can be produced by twinning, however. Many twinning modes have been reported for magnesium,' with (1012) twinning the most common and relatively easy to activate. Magnesium can deform by (1012) twinning when stressed along the c axis jn tension, but not in compression. In contrast, (1011) twinning is activated by compression along the c axis and not by tension. In addition to primary twinning, secondary twinning or slip can occur within the reoriented material of primary twins.' In general at least five independent shear systems must be active to bring about an arbitrary shape change such as that in the individual grains of a deforming polycrystalline material.' Because basal slip can_ provide only two independent shear systems and (1012) twinning can only accommodate an extension of the c axis, other deformation modes must be active in magnesium for an arbitrary shape change to occur. The purpose of this investigation has therefore been to study the various deformation modes in magnesium at room temperature, with special emphasis on those modes that are less easily activated. The effect of the alloying elements, thorium and lithium, has also been investigated. In polycrystalline aggregates, unambiguous identification of deformation modes is extremely difficult and the direct evaluation of the resolved shear stresses to activate them is not feasible. On the other hand, uni-axial tension and compression experiments on single crystals may not activate some of the- deformation modes because basal slip and/or {1012) twinning cannot be suppressed in most orientations. However, it should be possible to activate all possible deformation modes using oriented single crystals and plane-strain compression. Identification of active deformation systems and evaluation of the resolved shear stresses required to activate them should be facilitated. Wonsiewicz and Backofen have recently completed an investigation of the plasticity of pure magnesium crystals at various temperatures utilizing plane-strain compression and selected crystal orientations. This technique has also been used in the present work. The seven orientations selected for study are indicated in Table I. Plane-strain compression along the c axis (orientations A and B) should activate some deformation mode _other than basal, prism, or pyramidal slip, or (1012) twinning. In orientations C and D, prism or pyramidal slip would be expected to take place. When the compressive load is applied perpendicular to an unconstrained c axis (orientations E and F) the three slip modes should be suppressed but not (10i2) twinning. In orientation G, basal slip should occur.

Jan 1, 1969

By C. A. LINDBERG

Several new methods have been developed on the Iron Range to remove the material adhering to truck bodies in freezing weather. A machine known as a Gradall, incorporating the features of digging both above and below the horizontal, digging angle of blade control, full revolving, travel almost anywhere, and operated by one man, has proven successful in trials at body cleaning. Several of these units are in use with great saving in box-cleaning costs and improvements in efficiency of the truck operation with full capacity boxes. In addition to their winter use, the same machines have been used for ditching and excavating in the summer with great saving. The latest method of combating this freezing problem is to carry the exhaust from the engine through the body, making use of the tremendous heat that is now being wasted. To do this, the present wood sandwich which is used between the bottom of the box and the wear plate is removed and replaced with angles or channels run lengthwise of the box and spaced to permit gases to flow between or through them and also provide a good sup- port for the wear plate. The channels or angles are cut a little short on each end to form a cross passage that permits the gases to flow through the area. In the front end, openings are made in the wear plate and connect to a manifold created by welding a plate across the whole front of the box, spaced from the original end by the original vertical reinforcing angles at that point. The body being described is for a Euclid truck which is the only truck that has been adapted to this body-heating idea to date. At the rear of the truck, the holes from the cross passage are made in the bottom plate of the body and lead into a triangular-shaped body cross member under the scoop end of the truck.

Jan 1, 1949

By P. E. Busby, C. Wells

FURTHER study of data used in determinations of 1—rates of diffusion of boron in austenite and 2—solubilities of boron in the a and phases of iron and steel' has provided an equation for the diffusion of boron in a iron. In brief, the previously published data were accumulated from the results of deboron-izing (and decarburizing) experiments carried out in the range of 700° to 1300°C. Diffusion coefficients (D?) for boron in austenite were calculated using the Grube solution of Fick's law. However, only solubility values were estimated from the discontinuous concentration-penetration curves, Fig. 1, which are characteristic of diffusion in two phases. Dr. Carl Wagner' has recently provided a solution for calculating D values from penetration curves of this type as follows: Cl1.1 —C8/C8- C11.1 = vp ? e ? erf (?) and D = ?/4?2 t where C11,12, C8, C11, and E have the values shown in Fig. 1. D is the diffusion coefficient, sq cm per sec; t is time of deboronizing anneal, see; and ? is a di-mensionless parameter. For a given diffusion experiment, the value of ? can be readily obtained by graphical solution from a plot of y vs the right-hand part of Eq. 1. D may then be evaluated from Eq. 2. The avplication of this solution to previously re-ported results, of which excerpts are given in Table I, permits the calculation of diffusion coefficients for boron in a iron. On the basis of these meager data, it is tentatively concluded that the diffusion of boron in a may be represented by the equation Da = 1011 e-92,900/RT where R is the gas constant, cal X 0C-1 X mol-1; and T is the absolute temperature, OK. Although the frequency factor, 106 sq cm per sec, is admittedly several orders of magnitude higher than expected, the value of Q, 62,000 cal per mol, appears reasonable and is, in fact, very similar to that for the self-diffusion of iron. It is pertinent to mention at this point that the value of Q obtained for the diffusion of boron in austenite by means of the Wagner solution is 19,000 cal per mol and is in excellent agreement with the value previously reported1 in the equation DT = 2xl0-3 e-21,000/RT [4] which was determined by the application of the Grube solution to other data. The fact that determined constants A and Q in the equation D? = A e-Q/RT were practically the same, independent of whether the Wagner or Grube solutions were used in determinations of D values, strengthened the authors' belief that the computed values of D (Table I) using the Wagner solution are reliable. The relative values in Eqs. 3 and 4 for the diffusion of boron in the a and ? phases, respectively, suggest that boron forms a substitutional solid solution in a iron and an interstitial solid solution in ? iron. The same tentative conclusion has been reached by McBride et al.3 on the basis of relative solubilities, atom diameter, and the size of the interstitial hole in a and ? iron. In connection with the data for test 14 listed in Table I, it is of interest to calculate the solubility of boron in a iron using the D value given by Eq. 3. As might be anticipated from the small movement of the interface in test 14, proper substitutions in Eqs. 2 and 1 give a low value, approximately 0.0004 pct B, at 850°C. Apparently at 835°C (test 13) it is possible to obtain 0.0018 pct B, and at 850°C only 0.0004 pct B into solution in the a phase before a second phase appears. These observations are consistent with the Fe-B constitution diagram proposed by McBride, Spretnak, and Speiser.3 References P. E. Busby, M. E. Warga, and C. Wells: Diffusion and Solubility of Boron in Iron and Steel. Trans. AIME (1953) 197, p. 1463; Journal of Metals (November 1953). 'W. Jost: Diffusion in Solids, Liquids, Gases. (1952) pp. 69-71. New York. Academic Press Inc. "C. C. McBride, J. W. Spretnak, and R. Speiser: A Study of the Fe-Fe2B System. Trans. ASM (1954) 46, p. 499.

Jan 1, 1955

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By J. C. Reed

CINNABAR was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigel1 by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County-across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done con-siderable exploration work and has retorted the high-grade ore so .obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district.

Jan 1, 1935

By H. F. Seifert

THE classification and preparation of non-ferrous scrap metals is a subject of interest to every individual and corporation that employs in its processes of manufacture non-ferrous metals and alloys and accumulates in such manufacture scrap from these materials for disposition in the form of turnings, borings, short ends, punchings, clippings, grindings, washings, etc. All too frequently the disposition of such scrap is left to individuals who have no knowledge of the subject either from a metallurgical or a commercial standpoint, or both. Much money is thus lost which with a little more intelligent effort might be saved, and in this day of fierce competition and small profits such an opportunity cannot be ignored. The Mineral Resources of the United States for the year 1925, the latest issue available (Part 1, page 221), gives the secondary non-ferrous TABLE 1.-Some Secondary Non-ferrous Metals Recovered in the United States for the Year 1924-25 Material Short Tons Value Copper, including that in alloys other than brass.... 250,600 $ 71,170,400 Brass, scrap remelted 242,300 56,270,800 Lead as metal 112,4201 39,477,100 Lead as alloys 112,460 Zinc as metal 61,430 11,359,000 Zinc -in alloys other than brass 13,300 Tin as metal 1 7,950 35,165,400 Tin in alloys 23,000 Antimony as metal 1 } 3;794,000 Antimony in alloys 10,839 Aluminum as metal 17,700 24 Aluminum in alloys 26,300 ,816,000 Nickel as metal 19 1 1,518,000 Nickel in non-ferrous alloys 2,109 Total 882,600 $243,570,700

Jan 1, 1928

By R. J. Mechin

TOP-SLICING was introduced in the Pachuca district in 1917 by T. C. Baker, at that time mine superintendent, of the Santa Gertrudis mine. There then existed 1200 ft. (365.7 m.) below the surface, lying between the fourteenth and eighteenth levels (a vertical distance of 108 meters) a block of ore having a length of 295 ft. (90 m.), and an average width of 82 ft. (25 m.) and dipping at an angle of 65°. This block lay in the hanging wall of the vein and consisted of highly altered and fractured andesite, cut through with mineralized quartz stringers. On the foot-wall side, 26 ft. (8 m.) of old filling, left by former operators, was of payable grade. Stoping therein was first undertaken by the square-set filling system, but because of the extremely heavy hanging wall and loose dry filling in the foot wall, all square setting had to be accompanied by spiling, which made the operation exceedingly slow and costly. A system of mining was sought that would eliminate the difficulties inherent to the square-set system in heavy ground and that at the same time would effect the desired economies in mining. After several years, top-slicing has met all the conditions most satisfactorily, so that when similar conditions presented themselves in El Bordo mine, this method was adopted with necessary modifications. El Bordo mine is operated by the Santa Gertrudis company, and is situated about two miles north of Pachuca. Because of the diversity of the orebodies, a number of different mining methods are in use, among them top-slicing.

Jan 10, 1925

By Howard N. Eavenson

DURING the past year, as in the preceding ones, prices continued to fall, production to decrease, and more mines were closed. Much attention is being given by the industry to suggested plans for betterment of its position, and if the scheme recently brought out for consolidation of sales agencies into district agencies is loyally carried out, it cannot but help to improve conditions. The progress in the anthracite industry is shown in the report of its chairman, E. H. Suender; changes in coal preparation are outlined in the report of J. B. Morrow, chairman of Committee on Coal Preparation, while increased mechanization of the western mines is described by Eugene McAuliffe, chairman of the Committee on Machine and Strip Mining. In spite of the depression, interest in the Coal Division has been increasing, its meetings have been well attended, and its committees are active and have been doing excellent work.

Jan 1, 1932