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By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By Alten F. Grandt

Surface mining consists of the removal of the geologic strata overlying the coal seam usually with large electric shovels, draglines or bucket wheels. The method produces more or less parallel ridges or peaks of cast overburden, usually called "spoil banks". The mined lands vary widely in their inherent characteristics to produce a vegetative cover and thus can be put to a wide variety of uses. Use is the key to economic and social benefits. Physical and Chemical Characteristics of Soil Material of Surface Mined Lands after surface mining operations, the soil material is a heterogeneous mass whose physical and chemical properties are dominated by the character of the geologic strata overlying the coal. These strata are highly variable in thickness and character. They may include the surface soil, loess, glacial till, sands, shales, slates, limestone and sandstone rock. The method of mining with the several types of mining equipment will also affect the resultant mined area.

Jan 1, 1968

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By J. L. Reuss

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

Jan 1, 1968

By W. H. White, A. J. Sinclair

"Unaltered biotites from three samples of monzonite and gabbro from the Copper Mountain stock and a single sample from a pegmatic biotite-chalcopyrite vein cutting the Triassic Wolf Creek formation have a mean K-A age of 193±7 m.y. These data support a suggestion based on geological evidence that Copper Mountain ore deposits are related genetically to the Copper Mountain stock.A cogenetic mineral pair (biotite and clinopyroxene) from a sample of sericitized and chloritized monzonite of the Copper Mountain stock have identical K-A ages of 150 m.y., which probably represents a time of wide-spread, post-ore, hydrothermal alteration. This alteration is believed to be related genetically to a group of post-ore intrusions known as the ""mine dykes,"" suggesting that they also have an age of 150 m.y."

Jan 1, 1968

By Stanford O. Grodd

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

Jan 1, 1968

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By C. W. Hoffman

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

Jan 1, 1968

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5'7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

By Forrest T. Moyer

Injury experience at metal mines and mills (excluding officeworkers) in 1964 was 60 fatal and 3,672 nonfatal disabling work injuries during an exposure time of 149 million man-hours worked. These injuries occurred at a frequency rate of 24.57 per million man-hours and had a severity rate of 3,687 days lost or charged per million man-hours. Employment at 2,363 metal mines and 291 mills, excluding officeworkers, was 68,140 men in 1964. The average number of days worked was 274 The principal cause of fatal injuries at all mines and mills was haulage accidents and in underground mines, only, was falls of ground. The principal cause of nonfatal injuries was handling material accidents. The frequency rate at metal mines and mills in 1964 was slightly below that of 1963, whereas the severity rate was higher. Injury experience at 94 primary nonferrous smelters, refineries, and reduction plants (excluding officeworkers) was 8 fatal and 999 nonfatal disabling work injuries during a worktime of 98 million man-hours worked. The combined injury-frequency rate in 1964 was 10.29 and the injury-severity rate was 1,005. The 36,956 employees worked an average of 329 days during 1964. The principal cause of injuries at these plants was handling material accidents.

Jan 1, 1968

By T. N. Williamson

6.3-1. Historical Development. Rotary drilling has been used in surface mining for many years. Its principal use is for primary blasthole drilling. In this use, holes in the range from 4 to 15 in. in diameter are drilled in overburden and massive ore bodies for large initial blasting operation. With properly designed shot patterns and loading, secondary blasting is seldom required. The use of rotary drilling with diamond bits for exploration is discussed in Chapter 3.1. Small rotary drillholes of approximately 2-in. diameter are employed as blastholes to shatter uncovered coal seams, but this is a minor part of surface mining drilling operations. Another minor use of rotary drills in surface mining is for placing wire saw poles in dimension stone quarries, usually accomplished with large-diameter calyx or steel shot drills. Primary blasthole drilling by the rotary method was performed with drag bits until 1949 (19). Its use in mining was only in soft formations, so that rotary drills prior to that time were found principally in overburden drilling for the surface mining of coal. In 1949 it was found that air circulation to remove cuttings resulted in increased penetration rate and prolonged life for the rolling-cutter type of bits. Prior to that time, and since their introduction in oil well drilling in 1907, water had been used for circulation with these bits. The dependence on water to clean the hole had delayed the acceptance of bits with rolling cutters in mines because of water haulage and freezing problems as well as the loss of water through cracks in the formation. After rolling cutters were introduced, subsequent improvements in tools made rotary drilling adaptable to harder formations (18). This system is now used in the hardest formations encountered in mining. 6.3-2. Principles of Operation. ENERGY. Rotary drills attack rock with energy supplied to the bit by a rotating drill stem, and infrequently by

Jan 1, 1968

By John Chipman

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

Jan 1, 1968

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

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

Jan 1, 1968

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

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

Jan 1, 1968

By 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&apos; 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&apos; 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.&apos;" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-&apos; 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.&apos; 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].&apos; 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