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Coal - Surface Mining Coal Preparation Coal Utilization Research and Development Health and Safety

Jan 3, 1976

By Robert E. Green, Edmund G. Henneke

The velocities of the three possible modes of elastic wave propagation have been calculated for single-crystal copper at 1-deg intervals throughout the standard stereographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy flux and specimen axes are presented as arrows drawn on stereographic projections. The orientation factors associated with dislocation motion on the primary slip system only and also on all twelve slip systems have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing wave resonant specimen have also been calculated. The results of these calculatians are compared with earlier calculations on aluminum crystals and the relevance of these results to ultrasonic attenuation measurements is discussed. GREEN and inton' have recently outlined a procedure for determining the orientation factors for dislocation damping in single crystals. The stress field associated with a given mode of elastic wave propagation is resolved on the slip systems in which it is assumed the dislocations are vibrating due to this stress field. Since, at room temperature, slip has been observed on a limited number of systems in fcc and hcp metal crystals, it is assumed that these systems are the appropriate ones to use for the resolving process. This procedure has been applied to aluminum crystals by Hinton and hreen' and to zinc crystals by Henneke and Green.3 In the present paper the modes of elastic wave propagation have been calculated for copper crystals possessing orientations at 1-deg intervals throughout the standard stereographic triangle. The deviation of the energy flux vectors from the specimen axis have been calculated for each mode. The stress field associated with each mode has been resolved on the (111)(110) slip systems in order to determine the orientation factors for dislocation damping. MODES OF ELASTIC WAVE PROPAGATION For any direction in a linear homogeneous aniso-tropic material three elastic modes can be propagated. In general, each of these modes has both longitudinal and transverse particle displacements associated with it and thus are not "pure" modes. However, there is always one component which is greatest in either a longitudinal or transverse direction and hence the mode may be referred to as quasi-longitudinal or quasi-transverse, accordingly. For certain axes of high symmetry pure modes may be propagated. The phenomenon of refraction of the energy flux vector is also exhibited by elastic wave propagation in ani-

Jan 1, 1969

By Sherwin F. Kelly

THOUGH the Geophysics Commit- tee limited itself to two sessions this year, both of them marked by a high percentage of absentee authors, even this situation failed to dampen the and or of the ebullient geophysicists, who bandied no small amount of good- humoredlv barbed discussion. Hans Lundherg offered some constructive criticism of last year's report by the Geophysics Education Commit- tee, making a plea for more training in field techniques and less insistence on rigorous theoretical training. Carl Heiland pointed out the necessity of making geophysics and geology courses more attractive in order to draw more students into these fields. Exception was taken to this line of reasoning by Father Macelwane and Sherwin F. Kelly who emphasized the necessity for sound basic training if competent geophysicists were to be turned out. This discussion developed apropos of the report of the Geophysics Education Committee, which had been postponed from the Education Division meetings, but was not read as it was available in mimeographed form. Except for this diversion the morning program fol-

Jan 1, 1944

By R. D. Nelson, S. D. Dahlgren

The conditions of temperature, strain rate, and total strain favoring deformation by grain boundary sliding, slip, or deformation with concurrent recrystallization were evaluated for alpha plutonium. Grain boundary sliding and slip were studied by examining structures formed on polished surfaces with 4.5 pct compressive deformation. The conditions required for recrystallization were determined from compressive deformation us time curves. At 110" C and at a strain rate of 10&apos;per min, deformation was almost exclusively by grain boundary sliding whereas slip was the predominant deformation mode at -10°C and lo-&apos; per min. Defarmation at intermediate tenzperatures and strain rates produced structures showing mixtures of grain boundary sliding and slip. Recrystallization occurred concurrently with deformation only after a critical strain was reached. About 14, 6, and 3 pct strain was required at 105", llO°, and lZO°C, respectively, before recrystallization started, irrespective of the strain rate in the range of lo-&apos;1 to 10&apos;4 per nzin. L HE temperature and strain-rate dependency of the modes of plastic deformation were evaluated for high-purity as-cast alpha plutonium. The techniques used to study slip and grain boundary sliding were similar to those employed previously for alpha plutonium by Bronisz and Gorum,&apos; and spriet.&apos; Recrystallization was investigated using the methods reported by Nelson.3 Bronisz and Gorum&apos; found that slip occurred on more than one slip system at room temperature, and suggested that grain boundary sliding also contributed to the deformation. spriet2 found that deformation was predominantly by slip at room temperature, and observed one to three orientations of slip traces in individual grains. In addition, he deformed polished samples at 10O° C, but concluded that the deformation character of alpha plutonium at 100° C and at room temperature were not essentially different. Several investigators reported that twinning was only occasionally observed.1&apos;2&apos;4 Nelson3 recently found in creep tests that high-purity alpha plutonium would recrystallize concurrently with compressive deformation at temperatures between 25" and 115°C. EXPERIMENTAL PROCEDURE Electrorefined plutonium having less than 300 ppm total impurities was received from Los Alamos Scientific Laboratory in the form of +-in. diarn cast rods. Major impurities were americium, <I00 ppm, and tungsten, (60 ppm. Less than 25 ppm each of other impurities were present. The rods were cut into right half-cylinders 0.35 in. long and 0.25 in. in diam, and the flat faces along the cylinder axes were metal-lographically polished. To avoid loss of the metallo-graphic polish by oxidation, the polished samples were deformed in a silicone fluid heat treating medium contained in a chamber evacuated to a pressure of lo-&apos; torr. Deadweight loading was used to compress the samples between 4.5 and 20 pct at strain rates between 10"4 and lo- &apos; min-&apos;. Strain rates were determined by dividing the total deformation by the elapsed time of the test, even though the strain rate was not constant during deformation. Curves of strain vs time for samples deformed with a constant compressive stress3 show that the strain rate changes by less than a factor of four during the testing of a given sample, which is small compared to the three orders of magnitude change in strain rate investigated. Two samples were loaded into an ordinary metallographic mounting mold and impacted by striking the mold piston with one blow of a 2-lb hammer. Deformation temperatures for the two impact samples were 25" and 90°C. The samples, following deformation, were washed in carbon tetrachloride and their polished and deformed surfaces were immediately inspected metallographi-cally. Subsequently, the deformation structures were replicated with acetate replicating tape for later electron microscope examination, and the samples were then repolished and etched to reveal the microstruc-tures of the deformed metal. Second-stage carbon replicas were prepared from decontaminated acetate replicas using the procedure developed by Miller, Bierlein, and astel.&apos; Additional samples, which were 0.35 in. long by 0.25 in. in diam, were used to obtain constant load deformation vs time curves. These samples were deformed 10 to 20 pct with loads of 15 and 20,000 psi at 120°C; 30, 45, and 55,000 psi at 110°C; and 20 and 30,000 psi at 105°C. Samples were polished and etched to determine whether or not recrystallization or twinning had occurred during deformation. RESULTS AND DISCUSSION The experiments showed that alpha plutonium deforms by grain boundary sliding, slip, and deformation with concurrent recrystallization. Deformation by twinning was insignificant. Metallographic examination of polished and deformed surfaces revealed grain boundary sliding and slip. The start of recrystallization was ascertained from constant load deformation vs time curves. Deformed surface structures of samples compressed 4.5 pct under four different conditions of temperature and strain rate, Fig. 1, show how the deformation mode changes from predominantly grain boundary sliding to predominantly slip with increasing strain rate and decreasing temperature. Deformation at 110°C and 10" 4 min-&apos;, Fig. l(a), was predominantly by grain boundary sliding. Only a few slip traces can be seen in Fig. l(a).

Jan 1, 1969

By Alan Arias

On grinding in pure water, zirconium, tantalum, iron, and stainless-steel powders were extensively comminuted and simultaneously oxidized with hydrogen release, whereas nickel, copper, and silver powders did not react with water and their particle sizes increased. On grinding nickel, copper, and silver in water pressurized with oxygen, nickel and copper became extensively comminuted and were oxidized, whereas silver did not react with oxygen and its particle size increased. From these results and other considerations , it is hypothesized that for extensive comminution of ductile metals and alloys to occur on grinding they must react with the grinding media. UlTRAFINE metal and alloy powders are finding an ever-growing number of applications in metallurgy and in other fields.&apos; Of particular interest are ultrafine metal and alloy powders suitable for dispersion strengthening.2&apos;9 Various research programs on dispersion strengthening are being carried out and in some of these programs the ball-milling method is being used to produce dispersion-strengthened materials. This method usually involves the simultaneous grinding of metal or alloy and a dispersoid followed by consolidation of the resulting powder mixture. To obtain the ultrafine powders required for dispersion strengthening,&apos; grinding is carried out in many liquids, including aqueous and nonaqueous media, with or without grinding aids.4&apos;5 Nonaqueous liquids usually contain water as an impurity and some grinding aids may contain water of hydration.5 The water present may affect the grinding process. The writer has shown5 that. on ball milling chromium in water, the chromium is oxidized and hydrogen is released. It was surmised that the same reaction may occur on ball milling other metals and alloys in waterbearing liquids. Therefore, the investigation of ball milling in water was extended to metals and alloys other than chromium. In the course of the investigation, however, it became apparent that the data-to-gether with the results from a few additional experi-ments—could be used to postulate a comminution mechanism for ductile metals and alloys. A well-known comminution theory is that of smekal.7 According to this theory, comminution is possible because of the weakening effects of surface cracks and other imperfections in materials. This theory imposes a lower limit of about 1 µm for the ground particles. The beneficial effects of liquids and additives on the rate of grinding are well known.8 Mechanisms by which liquids and additives may aid in grinding were reviewed by Rose and Sullivan.&apos; One aspect of these effects is based on Rehbinder&apos;s theory of crack propagation in materials under stress.9 According to Reh-binder&apos;s theory, liquids or additives may promote the spread of cracks in stressed materials by lowering the surface tension at the crack tip. Rose and Sullivan surmise that the same mechanism may be operative during grinding, thereby facilitating comminution of the particles. In addition, Rose and Sullivan reviewed how additives may act as dispersants as a result of their being adsorbed on the surface of the particles being ground. This concept has been suggested by Quatinetz, Schafer, and smea15 to explain from their experiments the major role of additives that enabled them to grind metal down to 0.1 µm. Discussions of other comminution theories and additional sources of material on the subject will be found in Ref. 10. None of these previous suggestions and theories, however, can account for all phenomena encountered during ball milling of metals to submicron size in this and in a previous investigation by the author.6 The objectives of this investigation were to determine the behavior of metal powders during ball milling either in pure water or in oxygenated water and to gain an insight into the grinding mechanism. Zirconium, tantalum, iron, nickel, copper, and silver powders were ball-milled in pure water. These metals were selected because their oxides cover a wide range of free energies of formation. For comparison purposes, an alloy-type 430 stainless steel-was also ball-milled in pure water. The pressure of the hydrogen released during ball milling was monitored in order to determine the oxygen that combined with the metal or alloy. In order to obtain more information on the nature of the grinding process, nickel, copper, and silver powders were also ball-milled in oxygenated water (water pressurized with oxygen). The oxygen that reacted with the powders was determined from the pressure decrease in the mills. The powders resulting from ball milling in pure water and in oxygenated water were subjected to surface area, optical microscopy, and X-ray diffraction analyses. With these data, the oxygen calculated to be combined with the metals during ball milling, and comparison of the free energies of formation of the oxides of the milled powders with that of water, a comminution mechanism was postulated. MATERIALS, EQUIPMENT, AND PROCEDURES The materials used in this investigation were powdered metals, deaerated distilled water, high-purity helium, and commercial grade (99.5 pct purity) oxygen. The powdered metals used were zirconium, tantalum, iron, nickel, copper, and silver. A 16 pct Cr, ferritic stainless steel, type 430, was also used. The purities (or nominal compositions) and the surface areas of these metals and the alloy are given in Table I.

Jan 1, 1970

By Janshi Sen

VERTICAL-INTENSITY magnetometers, such as the Hotchkiss Superdip and the Askania vertical field balance, are now [ ] widely used, because vertical-intensity charts give definite information for the location of upper pole, dip and strike, and approximate shape of the deposit. Again, a slow and steady increase of dip over a large area indicates a large deep-lying deposit, while a large dip limited to a small area and falling away rapidly suggests a small and shallow one. The complication comes more from the richness of the ore. A large body of lean ore near the surface might produce the same vertical-intensity chart as a rich ore at depth. This paper presents a method for calculating the maximum depth of a single-pole deposit and another for a two-pole mineral body, by utilizing data of both vertical and horizontal intensities as obtained by a Thalen-Tiberg magnetometer. As shown on the left side of Fig. 1, lean ore, rich ore and a single pole produce the same magnetic field. The depth of the pole, [ ] h, can be calculated from the following relation: [h=a=tan¢=G-F h=aXFy] where G is the vertical intensity at point A due to the pole; F, the horizontal intensity of the same; and a, the distance from the point of maximum vertical intensity or the vertical projection of the pole on the surface to the point of observation A. If an entirely covered deposit is indicated by magnetic measurements and boring cost estimated from the calculated depth is so reasonable as to encourage drilling, the ore should be struck somewhere within the limit of the calculated depth by the borehole. A number of such points as A should be taken for calculation, erratic results should be rejected and the average figure used for cost estimation.

Jan 1, 1944

By J. B. DILWORTA

Ix estimating the investment-value of a mining-property or plant, the value of which decreases with operation, it is often necessary to know the sum which must be set aside periodically from earnings either to renew the plant at the end off its life, or to return the capital involved when the earning-power of the investment has ceased. In such cases it is manifestly incorrect simply to divide the total amount to be retired by the number of periods (usually years) during which the investment shall be active, as the sums periodically withdrawn have a certain interest-earning power varying with the length of time they are held and with the opportunities afforded for their investment. But though the interest may be considered to accumulate regularly year by year, yet the rules and tables for compound interest do not apply, owing to the addition of a fixed amount of new money to the total at the beginning of each period. Briefly stated, the problem of sinking-funds is, to find the amount of money which must be periodically set aside at a certain rate of interest, regularly compounded, to yield a certain sum in a given, length of time. In most practical cases the interest is compounded and the fresh amount added at the same time-usually once a year-and on this basis the problem may be solved as follows

Nov 1, 1909

By Robert J. White

Strong&apos;s equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong&apos; published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong&apos;s paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By C. R. Knopp

Gas-oil relative permeability ratio is an important relationship in oil reservoir predictive calculations. A correlation has been developed from 107 gas-flood k/k tests on Venezuelan core samples. The correlating parameter is based on restored-state water saturation tests and&apos; is applicable to both consolidated and poorly consolidated sandstone reservoirs. Data of the correlation show that there are no distinguishah1e differences between the mass-data groupings for the two c1assifications A procedure is recommended for running .sufficient relative. permeability analyses to compute a geometric mean of the sample group. The geometric mean is more representative of the total core, and probably the entire reservoir. For example, while only one in four of the k,,/k,., test curves agreed closely with the resultant correlation of this report, the geometric mean curves of the 16 suites (three samples or more). showed good agreetment ill three cases out of four. INTRODUCTION The gas-oil relative permeability ratio is an important, fundamental relationship in most oil reservoir predictive calculations. Predictive calculations are made to estimate future reservoir production characteristics and ultimate oil recovery. The k1,/k2, relationship is specifically needed to relate the surface gas-oil ratio to the reservoir oil and gas saturation, and to calculate the relative movement of these phases within the reservoir whenever some of the more complex driving mechanisms are present. Laboratory k1/k2, tests are not generally run as a routine analysis. Consequently, k1/k2 data often are not available when needed because the cost of laboratory work could not be justified or the need for such data had not been properly anticipated. When laboratory k1/k2, data are available, they are often very difficult to interpret. For example, wide divergence is sometimes shown in a family of k1,/k1, tests representative of the producing horizon in a single well. With these considerations in mind, a study was made to determine if a relationship might exist between the k1,/k2, curve and some other simple laboratory test criteria. The most probable k1/k2, curve correlation for Venezuela described in this paper is the result of the investigation. The presented correlation defines the most probable gas-flood k,,/k,, curve through the medium of air-water capillary displacement and centrifuge water saturation tests. The laboratory procedures of these tests are. relatively simple, and inexpensive; test data should be. widely available- from routine analysis. DATA AVAILABLE, LABORATORY METHODS The report correlation utilized 107 gas-Hood k1/k2, tests run on sandstone cores of Venezuelan reservoirs. Table 1 is a general tabulation of data pertinent to the tests, while Table 2 summarizes the data. Thetests include 96 from Western Venezuela and 11 from Eastern Venezuela. Eighty-two- of the 107 test samples were sandstones that varied from poorly consolidated to-unconsolidated; 25 were consolidated. The average sample porosity was 26.7 per cent and the average permeability was 1,121 md; these values typify the better sandstone reservoirs of&apos; Venezuela. The Welge gas-flood technique,&apos; based on fundamental Buckley-Leverett frontal displacement theory, was introduced in about 1952 and is widely accepted in the industry. The laboratory procedure is relatively simple, rapid, and can be performed on small core samples. While there have been some minor variations in sample preparation and laboratory procedure in the tests used for the correlation, these tests can be generally summarized as follows. The core sample was first sol vent-extracted and dried. Connate-water saturation was restored by the oil-flushing or evaporation-blow down methods. At the beginning of gas flood the hydrocarbon pore volume was completeiy saturated with the test oil phase. Unsteady-state gas-oil displacement then began with the injection of nitrogen or helium. while the displaced oil and gas phases were incrementally metered at the out-flow face. From the test data, the k,,/k,, curve was calculated by the Welge method.&apos; The individual oil and gas relative permeabilities were also calculated." CORRELATING PROCEDURES In attempting to establish a basis of correlation, we found that broad mid-range sections of 105 of the 107 k,,/k,, test curves could be closely duplicated by a straight line. Only two curves did not show a degree of linearity in this region. Correlation-curve definition parameters were subsequently developed from this observation of consistent mid-range linearity. Possible correlating variables were limited to the physical properties measured on core samples that (1) were widely available as common test data and (2) could be easily and cheaply obtained through future laboratory work. The more obvious possibilities were porosity, permeability and

Jan 1, 1966

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.&apos; Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.&apos; Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By B. J. Nelson, F. N. Rhinos

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a&apos; continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By F. N. Rhinos, B. J. Nelson

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a&apos; continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By C. R. Kuzell

IN COMPARISON with recent years 1932 has yielded much less tangible evidence of progress in copper reduction and refining. The industry has been extremely quiet, especially in the United States. Design and construction has been throttled by lack of new capital expenditures. The excess producing capacity of the whole industry and the extremely gloomy outlook for the future have made it unwise to tie up more capital except under special conditions. The plants built during the previous year have, however, been placed in operation. Older plants have been abandoned, temporarily shut down, placed on part time operating basis, or continue to operate at a low percentage of normal capacity. In the United States the Phelps Dodge Corporation at Douglas, Ariz., has completed the remodeling of the former Calumet & Arizona smelter. A new roaster and Cottrell plant chimney was completed this year. Though operations have been limited the new equipment has been found to justify all expectations. The reverberatory plant addition consists of two furnaces 26 by 107 ft. inside dimensions, with a high arch, and modern steel binding of excellent design. Natural gas fuel gives good results. One of these furnaces will treat 1000 tons of solid charge per day with a fuel consumption of approximately 3,000,000 B.t.u. per ton. The larger converters have not only yielded the expected lower costs, but have simplified operations in the converter department. One of the noticeable results is the greater cleanliness in the environment and the absence

Jan 1, 1933

By C. H. Green

. RECENTLY two papers on the structure of eutectics were read before the British Institute of Metals, one by F. L. Brady1 and the other by A. Portevin.2 In the preparation of photomicrographs of laboratory specimens as illustrations for student work, and in connection with various researches; the writer has been working along the same line for some, time and, therefore, was much interested in the results given, especially those of Portevin. He has correlated the information on the subject and has outlined a broad scientific basis for future work along this line. It is largely with the idea-of adding something by way of illustration to the work already done that this paper is written. The eutectic is generally understood to mean the alloy having the lowest melting point of any alloy of the system, and in which the melt becomes supersaturated with reference to the two or more phases which, separate out simultaneously (or alternately). From the surface pattern, the eutectic means; a structure with no primary crystals. It is not always easy to get the exact eutectic composition in making any alloy; in fact, a slight range in composition may be expected and some of the coarser particles may be richer in either of the composing metals. Even when chemical analysis shows the right composition, differences in density of the pure metals may cause segregation, or. supercooling resulting from different crystallizing properties may give a surface pattern the appearance of being on one side of the eutectic point. However, the alloys on either side of the eutectic composition, showing primary crystals of one of the phases and the effect of the pro-eutectic form on the surface pattern of the eutectic make a very interesting study, which is slightly touched upon in this paper. The phases, or microconstituents, of a eutectic may be pure metals (Pb-Sb, Tl-Au), solid solutions (Cd-Zn), a pure metal and a solid solution; (Ag-Sn), or a pure metal or solid solution with an intermetallic compound (Sb-Mg, Sb-Cu, As-Cu, Bi-Te, etc.).

Jan 2, 1925

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.&apos; colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2&apos;3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Richard W. Lodge

Mr. H. R. Batcheller, of the class of 1894, Massachusetts Institute of Technology, while experimenting with chlorine gas on a certain lot of roasted concentrates, met with the following difficulties: 1. A poor extraction of the gold. 2. A very large consumption of chlorine gas. 3. Inability to precipitate all of the gold from the solutioil containing the AuC1,. 4. The bullion obtained was very base. These difficulties were the same whether the chlorine was generated from H2SO47 MnO29 and salt, or whether H2SO, and bleaching powder were used. They may be accounted for partly by the presence of some arsenic left in the roasted ore, and partly by the presence of copper in the solution containing the AuCI3. It was therefore suggested to try the effect of bromine on a similar lot of ore. The use of this element is, of course, nothing new, but in the following experiments it seemed to present many advantages over chlorine. The material worked upon consisted of some concentrates containing 2.31 ounces of gold per ton, and 34.26 per cent. of arsenic, which would correspoild to about 74.4 per cent. Of

Jan 1, 1896

No. 264. A long established company operating steel and iron foundries, machine and forge shops, whose varied products are sold to the Government, railroads, mining and contracting industries, etc., has, openings in both manufacturing and selling departments for men with technical education and experience who are not subject to military call. State full particulars, kind of position preferred and salary expected. No. 265. Young man wanted, technical graduate preferred, to superintend construction f a small charcoal blast furnace. Man with blast-furnace experience preferred. For the right kind of man this is, not only a permanent job but an opportunity. In writing, give full particulars as to age, education, experience, salary wanted, etc. No. 26.6. An important copper mining and smelting company in Arizona needs two or three metallurgical chemists, at salaries. ranging front $150 to $175 per month. No. 267. A consulting mining engineer needs two superintendents for developing chrome deposits near Philadelphia; and another technical man for other engineering work in the same vicinity. No. 268. An iron-mining company, in New York State needs a mining engineer with knowledge of geology and acquaintance with construction work; A married man, with about 10 years&apos; engineering experience preferred.

Jan 2, 1918

By Francis Foley

IN examining steel under the microscope, one is constantly confronted with structures that are difficult to interpret. Recently, in a collection of samples for exhibition purposes, the writer found apiece of open-hearth runner metal, 2 in. (50 mm.) in diameter, that had been fractured for use as a sample of cast-steel structure. On polishing and etching a section for the purpose of photographing a field to typify the microstructure of steel in the "as cast" condition, a variety of structures was found (Fig. 1) so arranged as to arouse interest at once. For a distance of about 0.065 in. (1.6 mm.) from the skin of the runner, normal ingot structure was found (Fig. 2); this was followed by a zone, about 0.215 in. (5.5 mm.) wide, of considerably lower carbon content in which occurred a most pronounced Widmannstättian structure (Fig. 3); from this point on to the center of the runner, the metal was again of normal ingot structure (Fig. 4). Representative samples taken from the metal in the three zones showed the following analysis: C Ni Cr Metal from skin 0.34 1.26 0.63 Widmannstättian zone 0.21 1.18 0.63 Metal from center 0.34 1.32 0.67

Jan 7, 1919

By A. Perry Thompson

I. GENERAL DISTRIBUTIONS APPEARANCE, AND RELATIONS MINING in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,1 it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 4, 1915

By LUIS EAIYLNN SALAS

IF the ordinary wet method be attempted for silver-bullion containing tin, much trouble is experienced, varying with the amount of tin present. Even with a percentage as low as 0.05, the end-point is masked by a persistent turbidity, while with amounts ranging from 0.5 per cent. upward, the determination of the exact end-point is impossible, owing to the finely divided or colloidal metastannic acid resisting all efforts to cause it to settle, or to give a clear supernatant liquid. The object of the following experiments was to seek a remedy for these difficulties, and to find the conditions whereby the Gay Lussac method might be applied directly to these bullions. Material containing tin is met with frequently in bullion from Mexico or Bolivia; and tin is carried (sometimes in large quantities) in jewelers&apos; sweeps. 1. A bullion was prepared containing Ag, 74; Cu, 25; and Sn, 1 per cent. A weighed amount was treated by the humid assay-method as if it were an ordinary bullion free from tin. Ten cc. of HNO3 (1.21) was added, and the bottle was heated until all traces of red fumes had been expelled. Before heating, the solutions were moderately turbid; and after heating, the turbidity greatly increased. One hundred cc. of normal NaCl solution was added and the bottle was shaken vigorously at intervals during 30 min. The turbidity persisted. The bottle was allowed to stand over

Mar 1, 1912