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By A. B. Boghani, R. H. Trent

A computer program has been developed to simulate evacuation of a mine in various configurations. The simulation input variables include characteristics of the mine, expressed in the form of a network of passages, properties of hoists and hoisting strategies, initial miner positions, ventilation and compressed air velocities, stench warning system and self rescuer capabilities. The simulation can be carried out for cases in which there is no fire, i.e., fire drill simulation, or for cases in which there is a fire at any arbitrary location. The fire is assumed to generate gases which impede movement of miners in the gaseous region. However, the thermal effects of the fire are not considered. The simulation output include the evacuation time for each miner, movement of the hoists, propagation of smoke through the mine passages and smoke exposure of the miners. Several illustrative simulations have been carried out to verify validity of the program and to demonstrate its capabilities. The computer program has been able to predict evacuation time, within 5 percent, for an actual fire drill. It is believed that this program can be used to evaluate evacuation performance of a mine, identify problem areas and demonstrate improvements due to the recommended corrective actions.

Jan 1, 1977

By M. E. Wadsworth, P. H. Yu, C. K. Hansen

A study of the rate of dissc5lution of chalcopyrite (CuFeS2) in acidic solutions under oxygen overpressures was carried out by measuring the rate of formation of cupric ions in solution. Effects of temperature, oxygen partial pressure, surface area, and concentration of sulfuric acid were evaluated. A sized batch of chalcopyrite was leached in the temperature range of 125° to 175°C and in the pressure range of 75 to 400 psi of oxygen. In 0.5 N H2SO4 all products of reaction went into solution except for trace amounts of elemental sulfur. The dissolution of chalcopyrite followed linear kinetics and was essentially independent of hydrogen ion concentration for H2S04 concentrations between 0.2 and 0.5 N. The oxygen dependence indicated adsorption approaching limiting values with increasing oxygen pressure. The linear mechanism was explained in terms of steady-state adsorption of oxygen at the chalcopyrite surface followed by a surface reaction. The enthalpy of activation for adsorption of oxygen was found to be approximately 33 kcal per mole. An activation enthalpy of approximately 9 kcal per mole was observed for the surface reaction. Charge transfer reactions are not rate controlling in the process.

Jan 1, 1973

By S. M. Moos, R. E. Dugger

In reviewing available vacuum filtration equipment in this paper, several types of filters have been included which are probably not familiar to operators in the mining industry. However, it was felt that these units might be of interest in the event that an application should arise for the filtration of a product in the future that does not exist today. In addition, exposure of our industry to equipment used in other industries might have a tendency to be thought provoking and perhaps lead to the development of equipment and/or applications in our industry which do not necessarily exist at this time. Most innovations in filtration equipment have been confined to the improvement or design change of components and accessories, particularly reflecting the availability of materials of construction that have been developed. Recent developments in the application of horizontal belt filters have been innovative. The application of this unit as a substitute for or an adjunct to thickeners in a CCD circuit can certainly be innovative and perhaps provide a basis for reduction in capital and operating costs in this area. For example, mill tails are generally pumped at the highest possible density that will adequately flow. Tailings ponds and dams with their attendant design requirements are based upon this estimated water volume.

Jan 10, 1979

By E. S. Wheeler

THE rapid increase in the use of monel metal and malleable nickel in the form of sheet, rod and tube has resulted in a similar increase in the demand for these metals in the form of castings. These castings range in size from small valves and pipe fittings weighing a few ounces to large centrifugal pumps, gate valves and marine propellers, some of the latter weighing as much as 24,000 lb. A group of such castings is shown in Fig. 1. A large nickel agitator is shown in Fig. 2. FIG. 1.-A GROUP OF MONEL METAL AND NICKEL CASTINGS. Monel metal castings are widely used in accessories for steam power plants and in a variety of chemical plant. equipment where the corrosion resistance, high strength and toughness characteristic of this metal render it particularly valuable. Nickel castings find extensive use in the construction of corrosion resistant apparatus, and are often used in conjunction with wrought nickel sheet and tube in the fabrication of equipment for handling a variety of chemical and food products, particularly dairy products. In response to this demand for castings, numerous foundries have undertaken the production of castings of these metals and have met with varying degrees of success.

Jan 1, 1930

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By U. F. Kocks

SINGLE slip and a single parallel array of edge dislocations have been obtained in silicon single crystals by homogeneously bending them in a four-point dead-loading device at 1000°C around the [211] axis with [253.] as the tensile axis which encloses an angle of 40° with the glide plane. Other orientations or lower temperatures proved unsuitable. The homogeneity of the bending was checked by the method shown in Fig. 1. The chemically polished specimen was exposed to parallel light from a microscope-stage lamp. The sharpness of the focus of the reflected light is an approximate measure of the circularity of the sample. This method permitted the determination of the actual radius of bent specimens within 10 pct accuracy. The etching solution developed to show up dislocations consisted of the following volume parts: 2 HF, 1 HNO,, 2 CH,COOH, 1 a solution of 5 wt pct of CuNO, in water (Rosi'). The acetic-acid content was adjusted to produce fine well-defined etch-pits in about 2 min at room temperature. The effectiveness of the etch did not depend on the crystal-lographic orientation of the face etched. The number of etch pits produced after a given deformation was checked in the usual way against the Cahn formula' and showed good agreement. As it is to be expected from the orientation of the primary system there are slip steps on the top and bottom faces but not on the side faces (perpendicular to the bending axis), whereas etch pits appear on the side faces but not on the top and bottom faces. This is different only for occasional dislocations of a secondary glide system. All the micrographs included have been taken in places where the most of secondary glide could be seen. From this it is evident that in the homegeneously deformed region the number of secondary dislocations was less than 1 in 1000 of the primary type. Dislocation Distribution—A series of tests with varying amounts of deformation is shown in Figs. 2(a-c). An observation that can readily be made from these pictures is that the linear density of dislocations within slip lines is relatively constant and independent of the amount of deformation. "Slip line" in this context is understood to mean a line that is a straight connection of individual etch pits. The heavily pitted bands which can be seen in each of these three pictures may be resolved fairly definitely, at higher magnifications, into many "slip lines" the distance between them being of the order of 0.5p The distance between dislocations in slip lines is of the order of 2p and it is also fairly constant in going from the neutral zone outward. The higher over-all dislocation density in the outer regions of any sample and the higher total number in a more heavily deformed sample, are effected by a larger number of "slip lines." The relative constancy of the dislocation distance within an individual slip line is surprising. The absence of pile-ups" may imply, if there is no rear- rangement on unloading," that there are no substantial obstacles to slip in this case. It seems that the equilibrium distribution of the dislocations in each active slip plane under the higher external stress on

Jan 1, 1959

By A. D. Marlin, A. J. Gentile, E. F. Jordan

Metallurgical changes in SAE 52100 ball-bearing components resulting from overload testing are described. Changes in microstructure, hardness, and resiclctal stresses crre discussed zuitlz re.ference to material cleanliness obtained by various steel-melting practices and are compared with work by otlzer investigators. Evidence is presented to show that the initialion and development of microstruc-tural alterations are characterized by two separate reactions: the appeavance of a "dark etchingJ' constituent, and "gray lines" or a light etclzing constituent. The dependency of these tzvo reactions on material cleunliness, running tirne, and contact stresses is discussed and a failure mode related to material cleanliness and microstructural transformation is proposed. THE study of ball- and roller-bearing contact fatigue has been paced by a strong emphasis on bears ing application performance. Particular attention has been paid to conditions that effect the spalling-type failure that is characteristic of rolling contact fatigue in through-hardened components. Some of the conditions investigated are lubrication and atmosphere,1-3 material characteristics and finish,475 and speed and design fa~tors."~ A typical spalling-type failure is shown in Fig. 1. The arrow shows the motion of the ball relative to the inner-ring race surface. The leading edge of the spall is usually sharper than the trailing edge. The race surface near the trailing edge also shows small dents caused by debris from the spall. In this type of testing very little metallurgical investigation is done on failed bearings. Emphasis is placed on test conditions and statistical analyses of endurance data. More basic work has been done relating micro-structural changes to fatigue performance. Dyer" and Wood, Cousland, and sargant9 have used mostly simple materials, such as single crystals and single-phase polycrystalline specimens, under simple alternating strain to identify a systematic process of fatigue damage. drutowski" was concerned primarily with the relationship between steel structure, contact stress, and energy losses in rolling contact. dones11 and Bush, Grube, and Robinson12 utilized changes in microstructure and residual stress in overload-tested rolling contact elements as a means of investigating the fatigue process. Work is being done on an ASME-sponsored contract,13 using both simple and complex materials, but there is still a long way to go before such theories as pore and void growth in simple structures can be applied to the relatively complex bearing steel microstructure. The purpose of this paper is to report on an investigation into the effect of steel cleanliness on the structural alteration and residual stress changes found in overload-tested ball bearings. Using these results and those of previous investigators, we will propose probable failure mechanisms in both overload- and normal load-tested ball bearings.14,15 PROCEDURE Ball bearings? 3208 size, were fabricated from SAE 52100 steel obtained by five different melting practices. The melting practices, chemistry, and inclusion ratings for the five lots of steel are summarized in Tables I and 11. The nonmetallic inclusion ratings were determined by the Jernkontoret method described in ASTM E45-51 Method A. This technique consists of microscopically examining a series of polished samples taken from specified locations in the ingots, billets, or bars. Each sample is surveyed at XlOO magnification and the inclusion types and sizes are compared to standard fields. Because of the nature of these ratings all values in Table I1 are rounded to the nearest half. The elec-

Jan 1, 1965

By J. L. Huitt, IM. L. Slusser, E. E. Glenn, M. L. Slusser

This paper is concerned with: (1) an analysis and interpretation of the filtration characteristics of drilling muds on filter paper, and (2) an interpretation of early stage "filtration" on consolidated synthetic porous media, herein referred to as the "surge loss" period. It is shown that water-loss data can be plotted so as to disclose the existence of a surge period, a non-uni-form cake thickness period, and a constant pressure filtration period. The same periods occur during exposure of consolidated porous media to muds. The data on consolidated porous media indicate that: (1) mud particles bridge pores inside porous media during the surge period, and (2) "filter cake" build-up inside porous media occurs during subsequent filtration. The data also show that the surge loss increases with sample permeability and with pressure differential. INTRODUCTION The phenomenon of mud filtrate invasion into porous sands of a drilling well has been recognized for many years.1,2,3,4 Part of API Code 29 is concerned with the filtration testing of a drilling mud to yield data on this subject. In a number of investigations "plastering properties" of muds were studied,5,6,7,8 "plastering" apparently meaning cake forming properties. In such studies the characteristics (thickness, permeability, and toughness) of the cake and the rate at which the liquid phase of the mud was separated from the solids (filtration rate through the cake, commonly referred to as water loss) were measured or at least considered. From the standpoint of its effect on well productivity, filtrate invasion into "clean" water-wet pay sands (i.e., those containing no clay minerals) may not necessarily be a serious problem. An increase in water saturation in the zone immediately around the wellbore would cause loss of oil permeability. However, in such a system, much of this water may be removed by oil production. If filtration occurs into "dirty" sands (i.e., those containing appreciable clay minerals), clay swelling or other mechanisms may cause losses in oil permeability which cannot be overcome by oil production.'.' The phenomenon of mud particle invasion into the pay sand of a drilling well was considered to be a possible serious factor in the early days of rotary drilling. Opinions varied as to whether drilling fluids "mudded up" and "sealed" oil sands. In 1932 Rubel,9 Gill,10 and Parsons," in separate papers, presented differences of opinion together with some laboratory and field data concerning loss of oil production caused by drilling fluid invasion into pay zones. These papers, and the discussions, furnish a large background on this subject and indicate the very clear thinking of many men at a time when petroleum production technology was in its infancy. Jones and Babson,6 and Silent,' experimentally found that the depth to which mud particles invaded water-saturated sand packs was small (no greater than 1/16 in). Arn-quist12 in 1937 observed loss of water permeability due to invasion of mud particles into water-saturated, consolidated, sandstone samples. Williams and Cannon5 studied the filtra-tion properties of drilling muds and mentioned "sludge" which penetrated a short distance into the water-saturated filtering medium (sand pack). Byck5 concluded that formation permeability had no effect on the plas-

Jan 1, 1958

By R. H. Pemberton

The principle of airborne electroniagnetic prospecting is well-known. 'The basic geonhysicai texts in inost cases discuss the main elements involved in electromagnetic prospecting. However. there is ceriainlv iittle information available to the public concerning he present types of airborne eiectromagnerlc systenis being flown today by both contracting companies and some of the mining companies which have their own instruments. This is unfortunate since it is difficuit for those people not conducting such operations to understand thoroughly the iarge variation in the electromagnetic instrunlents available. Basically, the aeriai electromagnetic induction method utilizes a primary or transmitting coil through which is generated an alternating magnetic field at a frequents: generally of the range of 100 to 2000 cycies per sec. This primary field links with buried conductors and generates eddy currents within them. These eddy currents in themselves generate a secondary magnetic field of the same frequencv, but generally nut-of-phase with respect to the prinlarv field. This secondarv field is detected above the ground in the pick-up or receiver coil which is tuned to the frequency of the current applied to the primary transmitter coil. One of the main problems in the development of an airborne electromagnetic system is that of maintaining constant coupling between the cransmitting and receiving coil systems. Any variations in the coupling due to relative motion between the two coils will result in an in-phase signal being induced in the receiver coil. [However, any variation in the coupling does not result in an out-of-phase signal change in the receiver coil. The first airborne eiectromagnetic svsteins which were developed utilized a large prlniarv coil set up on the aircraft with the receiving coil being towed behind in a bird, generally at the end of a cable of about 500 ft. in length. It is possible with such a system to record the out-of-phase or quadrature responses more readily than the in-phase re-sponse. One system utilizes a dual frequency method, wnereby the out-of-phase responses at two frequencies are recorded. Another system used today records a single-frequency olrt-of-phase response. Recentlv home companies have succeeded in measuring from ne air both the out-of-phase and the in-phase components. The usefulness of recording in-phase is weil-known, but unfortunately this is difficult to obtain in any towed-bird system. In order to measure the true in-phase signal, the most straightforward system is that in which both the transmitter and receiver coils .Ire affixed in space so that there is little or no relarive motion between the two coils. THE FLIGHT SYSTEM The particular system which Canadian Aero Service is using at present is mounted on a Sikorsky S-55 helicopter (Fig. 1). A record of both the in-phase and out-of-phase responses is made at a frequency of 390 cycles per sec. The transmitter coil is set on a boom mounted in the front of the helicopter; the receiver is set on a tail boom extending back from the helicopter. Separation between these coils is about 65 ft. The two coils are mounted in a vertical co-axial relationship. Having the transmitting coil in a vertical plane ensures that maximurn coupling will occur with vertical conductors rather than flat-lying conductors. Having them mounted as they are in a co-axial relationship on the helicopter ensures that maximum response will occur when the flight direction is orthogonal to the strike direction of a given conductor. The present sensitivity of the Em system is 20

Jan 1, 1961

By J. Paces, E. Miller, K. L. Komarek

The resistivity was determined as a function of temperature over the composition range from pure cadmium to 40 at. pct Cd. Melts with cadmium contents less than 85 at. pct had negative temperature coefficients of resistinity. On cooling below a transition temperature close to the liquidus temperature, the slope of the resistivity-temperature curve changed sharply. The activation energy calculated from the slope was 0.07 ev above the transition temperature and 0.14 ev below. The resistivity vs composition curve shows two maxima corresponding in composition approximately to CdSb and Cd3Sb2. THE relationship between the structure of a liquid and that of the crystal formed on solidification is at present not well-under stood. Various experimental determinations of the properties of liquids indicate that deviations from random atomic arrangements in liquids occur and that the properties of a solid and of its melt are closely related. Thermody-namic activities of liquids usually show negative deviations in systems where compound formation occurs in the solid,' and X-ray data indicate that close-packed solids and their melts frequently have nearly the same coordination number. Electrical resistivities and viscosities of liquids frequently exhibit maxima at compositions corresponding to compounds in the solid state. It should be of interest to study systems which have both stable and metastable compounds in the solid, and to determine if the short-range order in the liquid is affected by the existence of the metastable solid phase. The Cd-Sb system exhibits such a metastable phase. The phase diagram is shown in Fig. 1.3 The stable system has one intermetallic compound, CdSb, crystallizing in the orthorhombic crystal structure, with a melting point of 456°C. The metastable system also has one compound, Cd3Sb2, melting at 420°C and crystallizing in the monoclinic structure. Metastable alloys transform to the stable crystal structure in the temperature range from 250o to 350°C. Several distinct indications of very strong short-range order in the liquid phase have been reported in this system, with a close relation between the ordering in the liquid and the existence of both the stable and metastable solid phases. Scheil and Baach4 have observed distinctly different vapor pressures for liquid Cd-Sb alloys depending on whether the liquid solidified to the metastable- or stable-phase configuration. They observed an unusually sharp increase of the activity in a limited temperature interval immediately above the liquidus temperature of stable alloys, followed by a sudden decrease in slope to what they considered normal values. On cooling, the activity data reproduced the values in the normal range but then deviated from the values obtained on heating. They also observed that specimens of the stable phase upon melting and resolidifying always crystallized in the stable crystal structure as long as the melt was not heated to more than 485° to 525°C; otherwise solidification to the metastable phase occurred. However, in a later investigation, these results were not reproduced (13). The resistivity of liquid Cd-Sb alloys has been investigated by Matuyama 5, Oleari and Fioram, 8 and Belaschenko (141, but only above 500°C, the temperature region where Scheil and Baach observed no vapor-pressure anomalies. The data of Matuyama and of Oleari and Fiorani are reproduced in Fig. 5 and show a maximum in resistivity at 50 at. pct Cd. The data of Oleari and Fiorani, however, show the maximum as being rounded, and their values in general are slightly higher than those of Matuyama.

Jan 1, 1964

By R. A. Swalin

IN this paper, the results of an investigation concerning the diffusion of three elements, magnesium, silicon, and molybdenum, in nickel are presented. The work represents a continuation of a diffusion program relating to solute diffusion in nickel. The program has the dual aim of obtaining useful diffusion data and of yielding insight into the factors governing solute diffusion in close-packed metals. The first paper of this series has been published earlier? In both investigations, in agreement with recent results from other laboratories, the activation energies for solute diffusion were found to be close but not identical to that of self-diffusion in the pure solvent in question. In order to obtain valid diffusion data, certain experimental pitfalls recognized only in recent years had to be avoided. Chief among these were the necessity for minimizing short-circuiting diffusion paths such as grain boundaries and the necessity for using low solute concentration gradients. In this series of investigations the following precautions were taken in an attempt to minimize such errors. 1) Samples with large grain sizes, 0.5 to 10 mm, were prepared. 2) The diffusion coefficients were measured at relatively high temperatures, since imperfections such as dislocations play a less important role at such temperatures than at lower temperatures. 3) Alloys containing less than 1 atomic pct were chosen for study. Experimental Work Materials—A diffusion couple technique was employed in the experimental investigation. Briefly, this technique consisted of the following. A diffusion couple was fabricated by placing a flat face of a cylindrically shaped alloy disk against a similar face of a pure nickel disk, and a bond was formed at an intermediate temperature under pressure. The diffusion couple thus fabricated was subjected to a diffusion anneal at higher temperatures for a measured period of time and then sectioned perpendicular to the direction of diffusion. After analyzing the sections for solute concentration the diffusion coefficient was determined from a probability, plot of concentration vs distance from the diffusion interface. Vacuum melted Mond nickel was used in the experimental program. The chemical analysis of this nickel is listed in Table I. Alloys used were prepared

Jan 1, 1958

By K. G. Davis, P. Fryzuk

VALUES for the equilibrium distribution coefficient, ko, are required for solidification studies. The procedure generally adopted1-3 is to progressively solidify alloy rods over a range of growth rates, under conditions where a high degree of convective mixing is present in the melt. The measured effective distribution coefficients are plotted as a function of growth rate, and the extrapolated value at zero growth rate is taken to be the equilibrium ko. The method is limited by the experimental difficulty in obtaining steady growth rates less than approximately 10-4 cm per sec. Extrapolation from rates greater than this can lead to inaccuracy. In the present investigation, an alternative method for determining ko, previously used by the authors for the Ag-Sn system,' was applied to alloy of thallium in tin. Specimens were grown under conditions where convective mixing was absent, and experimental concentration-distance curves in the region of the initial transient were compared with curves calculated for trial values of ko. The ko which gave the best fit was taken as the correct value. To obtain the calculated curves, a value for the diffusion constant in the liquid near to the melting point was needed. This was determined by the capillary-reservoir method. Diffusion Constants. Details of the experimental procedure used by the authors in the capillary-reservoir technique have been described in previous papers,5'6 the only variation being in the use of Tl204, a ß emitter, as tracer, in contrast to previous work where ? emitters were used. The activity of a ß-emitting sample, as measured in a Geiger counter, is proportional to the surface area. To measure the concentration of thallium along the capillary after diffusion had taken place, the solidified capillary (1 mm diam) was cut into 2.5-mm lengths and each length compressed between parallel steel plates to form a disc approximately 5 mm in diam. The discs were placed in a flat-bottomed dish, covered by a thin lead shield with a central aperture, and counted in a 0 counter with fixed geometry. Each disc was etched lightly in a dilute solution of nitric and hydrochloric acids a short time before counting, to eliminate sur-

Jan 1, 1968

By Harry Seltz

SEVERAL investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeser1 has made measurements of "average heat capacities" of iron carbide between 1026° and 85° K., using a water calorimeter. His computed true specific heat at 78.1° K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0° K. The cementite used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes" has measured the specific heat of iron carbide, from 102° to 323° K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100° K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3C, S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley' has reviewed these measurements and calculations, and selects those of Roth4 and Naeser5 as worthy of most consideration. Roth has given ?H = 5400 cal. ± 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (ß) he finds OH = 5600 cal. Kelley accepts the rounded figure ?H = 5500 as the heat of formation at 298.1° K., but this value is quite uncertain.

Jan 1, 1939

By Henry Seltz, Cyril Wells, Hugh J. MacDonald

Several investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeserl has made measurements of "average heat capacities" of iron carbide between 1026" and 85" K., using a water calorimeter. His computed true specific heat at 78.1" K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0" K. The cementitc used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes2 has measured the specific heat of iron carbide, from 102" to 323" K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100" K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3 C,S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley3 has reviewed these measurements and calculations, and selects those of Roth* and Naeser6 as worthy of most consideration. Roth has given AH = 5400 cal. + 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (0) he finds AH = 5600 cal. Kelley accepts the rounded figure AH = 5500 as the heat of formation at 298.1" K., but this value is quite uncertain.

Jan 1, 1940

By Henry Seltz, Hugh J. MacDonald, Cyril Wells

Several investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeserl has made measurements of "average heat capacities" of iron carbide between 1026" and 85" K., using a water calorimeter. His computed true specific heat at 78.1" K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0" K. The cementitc used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes2 has measured the specific heat of iron carbide, from 102" to 323" K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100" K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3 C,S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley3 has reviewed these measurements and calculations, and selects those of Roth* and Naeser6 as worthy of most consideration. Roth has given AH = 5400 cal. + 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (0) he finds AH = 5600 cal. Kelley accepts the rounded figure AH = 5500 as the heat of formation at 298.1" K., but this value is quite uncertain.

Jan 1, 1940

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.' The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By W. A. Tiller, S. O’Hara

Grain refinement in stirred melts has previously been shown to arise from dendrite segmentation. The present work discusses experiments capable of distinguishing between remelting and mechanical effects which result from fluid motion. Nucleation of still un-dercooled Sn-1 pct Pb melts with a single-crystal seed shows that the grain size of the resulting ingots decreases as the undercooling at nucleation increases up to about 1Z0C, then increases again for larger undercoolings. Pure melts exhibit little refinement as a result of nucleation at any undercooling up to 12°C. The presence of fluid motion gives rise to grain multiplication in pure melts, but the magnitude of this effect is partly obscured by solid-state pain growth. The results indicate that two grain-multiplication pvocesses can operate, one which involves dendrite remelt ing, and another associated with fluid motion. Small ingot experiments indicated that an equiaxed transition can be caused by fluid motion. THE presence of forced convection during recales-cence of undercooled Sn-1.3 pct Pb melts has been shown to give rise to extensive grain refinement during solidification of small ingots of this alloy.''2 In Ref. 2, this refining was shown to result entirely from dendrite fragmentation and not from any nucleation mechanism. The purpose of the present work is to establish what processes lead to dendrite segmentation. Experiments were therefore carried out to determine the resulting structure of both pure tin and Sn-1 pct Pb melts, nucleated at various undercoolings by single-crystal seeds in the absence of forced or natural convection. By comparing the information obtained from these experiments with the results of Refs. 1 and 2, the effects of fluid motion on the ingot structure, and the details of the segmentation mechanisms, should become clear. The results of these experiments should also be helpful in understanding the solidification structures of larger ingots since natural convection, which is known to play an important role in determining ingot structure13 differs only in degree from the fluid-motion effects studied here. I) EXPERIMENTAL PROCEDURE The apparatus shown in Fig. 1 was constructed to permit controlled nucleation of stirred or unstirred supercooled melts using a seed oriented in the tin dendrite growth direction. Because the melts, in all cases, were capable of larger supercoolings than the one used in each experiment, the structure observed always resulted from a single nucleation event at the surface. The sequential procedure was as follows: Tin was melted under purified hydrogen and the oxide removed at a temperature of 450°C . Electromagnetic stirring was then used to clear the surface completely and during this time the guide tube was lowered underneath the melt surface. A pointed Czochralski-like crystal was then propagated from a specially prepared tin dendrite seed4 inside the guide tube while the temperature of the bulk melt was held just above the melting point, ensuring a perfectly clean seed which was epitaxial with the original dendrite. The dendrite and epitaxial seed, still in the guide tube, were withdrawn from the melt which, in turn, was undercooled to 2C° below the temperature at which the nucleation experiment was to be performed. The melt was held there for several minutes, both in stirred and in still-melt experiments. The temperature was next raised to the required value and the melt nucleated by the carrot seed inside the guide tube, the heater power being shut off just after nucleation. In experiments where quenching after nucleation was required, a high-density graphite crucible was used, but otherwise the procedure was as described above. The temperature gradient in the melt before nucleation was kept below 1C° per cm by carrying the experiment out just below the center of the heater shown in Fig. 1.

Jan 1, 1968

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By M. Cross

INTRODUCTION The development of refining processes involving gas injection into liquid metals has seen the evolution of a variety of designs [I]. During the last few years or so the top, bottom and side blown processes have, essentially, been combined to produce a series of mixed gas blowing schemes (eg. the LBE [2,3] and LD-OB processes [4,5]). Although, a variety of mixed gas blowing processes have been carefully engineered and recorded operational experience now attests to their effectiveness, optimising their design and operational performance is another matter. Detailed process analysis of such operations is impeded by the complex nature of the physical and chemical processes involved: . fluid flow behaviour of the liquid metal and injected gases, . chemical reactions in the vessel, . mass and heat transfer within the fluid phases in the vessel, . influence of the geometry (eg. location of the tuyeres, etc.), . monitoring the operational performance. By and large, design and operating parameters evolve from a combination of laboratory scale experiments, pilot plant work and, of course, practical engineering experience. Conventionally, the gas-liquid system used to model the industrial process is air-water, for a number of valid reasons including – . visual demonstration plus geometric and (to some extent) dynamic similarity, . the fact that the system demonstrates, at least, qualitatively many of the complex features of gas injection - interaction between the gas and the liquid - the nature of the gas flow behaviour - qualitative indications of mass transfer rates Important experimental contributions to the understanding of gas liquid systems include the work of Brimacombe [6], Wraith [7], T.Robertson [8], D.Robertson [9], Guthrie [10] and Szekely [11] (these references provide starting points to identify the major published work in this area). Although air-water systems have been instrumental in providing a great deal of qualitative insight into the fluid flow behaviour of the processes, reliable quantitative predictions are more problematic. A number of workers (notably Brimacombe and colleagues [6, 12])have demonstrated that different gas-liquid systems can lead to wide variations in behaviour. Other limitations of physical modelling include the assumptions of isothermal flow, scale- up of turbulent flow behaviour and the inability to directly include the effects of chemical reactions. The above limitations in physical modelling, therefore, yield a natural role for mathematical modelling provided that it can be made comprehensive enough whilst remaining cost-effective. The major physical processes involved in gas injection systems may be summarised as . behaviour of the gas envelope structure in moving through the liquid metal . the global movement of the liquid metal . momentum interaction between the liquid metal and the injected gas . heat transfer and mass exchange via the chemical react ions. The behaviour of gas envelopes forming at a tuyere and then moving through the liquid has been investigated thoroughly by a large number of workers. Such models are generally based upon simple physic- al concepts derived from visual observation. An early model by Davidson and Schuler (DS), based upon a force balance between the liquid inertia and a combination of the bouyancy and momentum forces on the envelope, has proved to be a useful tool in predicting bubble volumes at detachment [13]. The DS model has been successfully modified in a number of ways [14-17] to cope with heat transfer and reactive transfer rates, etc. Furthermore, the basic ideas summarised above have also been confirmed on industrial converters by both Guthrie [I8] and Brimacombe [19]. Models have also been developed to predict the behaviour of the "chemical" component of some gas-liquid systems. However, one thing is clear; all gas-liquid reactive systems are governed by the degree to which effective mixing occurs. As such, the processes are dominated by the behaviour of the heat and mass exchange of the two phase fluid flow system. It is the pattern of movement of the turbulent liquid metal plus its interaction with the injected gas which must be predicted reliably, if sufficiently comprehensive comp-

Jan 1, 1984

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970