Search Documents

By Fred N. Kissell, Maurice Deul, T. D. Moore

Methane emission from two surface gob-degasification boreholes was measured by the Bureau of Mines. The investigation took place during mining of a 3,200-foot longwall panel in the Lower Kittanning coalbed in central Pennsylvania. The first hole was 500 feet from the start of mining, and the second hole was 2,200 feet. The first hole went on natural draft as soon as the longwall face passed it. This caused the methane flow in the return entries to drop 75 pct. In the 6 months required to complete the panel, the two holes emitted 69 MMcf of methane in varying percentages of concentration in air. In 3 years, the holes emitted a total of 150 MMcf of methane.

Jan 1, 1976

Minimize airborne respirable quartz dust produced by continous mining machines. Approach Install a shovel-mounted underboom water spray system on the off-curtain side of the mining machine. Dusty air containing quartz is momentarily trapped under the boom, where it is captured by fine spray mist. The remaining dust cloud is directed immediately behind the curtain before it can migrate back to the machine operator's location. How It Works Previous studies have shown that most of the dust generated by continous mining machines occurs under the boon as the cutter head shears down. The primary source of respirable quartz dust on many continous mining operations is cutting or trimming roof rock immediately prior to shearing. This results in very high concentration , of

Jan 1, 1989

By Donald Cummings

MEASURES appropriate for the control of the silicosis hazard in mining cannot be formulated precisely, but sufficient knowledge1-19 has accumu-lated during the past quarter century to permit the suggestion of useful, though partly empirical, rules for its alleviation. The industrial hygienist today recognizes that the peril incurred by the inhalation of harmful dust is a function of two variable factors-the degree of harmful exposure and the specific susceptibility of the exposed individual to pulmonary injury. Con-trol of the danger arising out of prolonged contact with pernicious air-borne particulate matter is consequently best exercised by influencing both of these recognized variables. Obviously the problem has two broad aspects-one, medical; the other within the province of the engineer.

Jan 1, 1938

By H. W. Young

Development of high-tension outdoor substations during the past few years has been due primarily to economic reasons. The demand for power in small communities could not be met with the conventional and Fig. 1.—33,000-VOLT step-up outdoor air-break switch and substation installation outside of a powerhouse generating at 2300 volts stepping up to 33,000. Twenty-one coal mines are supplied from lines leading from this installation. comparatively expensive indoor types unless the rate for service was materially increased. To prove that the problems lncident to development have been solved successfully, it is only necessary to point to the wide adoption of outdoor substations by utility companies. Passing at once to the question as to whether outdoor substations are applicable to

Jan 1, 1920

Laboratory trials were performed in an induction furnace to study droplet formation during lance blowing. Compressed air was blown on a molten iron bath consisting of iron alloyed with carbon and silicon. Steel droplets were collected using a specially designed sampler. The average steel droplet composition and the oxide layer thickness were determined using scanning electron microscopy combined with energy dispersed spectroscopy. In addition, the concentration gradient of elements was determined using a microprobe. It should be noted that a special technique had to be developed in order to prepare the droplet sample. The size distribution and composition of the droplets was also determined using the microprobe. It was found that the carbon content in the droplets was lower than the carbon content in the bulk.

Jan 1, 2006

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By Kikuo Matsui

In a difficult economic environment, the coal mines in Japan have been making extensive efforts in order to survive by rationalizing the mining operations. Introduction of a new longwall mining system is one of these efforts to establish the rational production structure. In the high production longwall mining system, gateroads should be developed rapidly and maintained effectively during their lifetime. Strata bolting support system has been employed in the gateroads to raise their stability levels and reduce their maintenance cost. However, excessive gatemad closure caused by longwall mining is still occurring, impeding the passage of equipment, personnel transportation, and ventilation air in the longwall panels. This paper describes the development system of gateroads and proposes a new mining method to control the excessive roadway closure problem.

Jan 1, 1995

Methane is present in varying degrees in nearly all underground coal mining operations. At mixtures with air near 5-15% it is explosive and consequently since it is not usual for these levels of contamination to be reached in the general body of a mine ventilation system it is not unusual to experience it in specific places. On longwall faces the most used power loader is the shearer machine and because of its general shape, situation and operation it is likely that all the factors which are required to cause a frictional ignition can be present. This paper makes a general appreciation of the causes of these ignitions and methods which are and have been used to control these situations on and around these machines.

Jan 1, 1981

By Wallman D

Since 1981 two single entry roadways have been driven at Ellalong Colliery for a total distance of 1 030 metres. They were driven at a height of 1.73 metres within the 3.7 metres thick Greta Seam using a Dosco In-Seam Miner (I.S.M.). Ventilation of the drivage was accomplish- ed by an exhausting fan in series with steel ducting and flexible ducting in the immediate face area. The air quantities provided at the face were more than adequate to comply with the requirements of -the auxiliary fan rules and the Coal Mines Regulation Act, 1912, as amended. The experience gained in these drivages demonstrated that the ventilation of long single entry headings can be practically and safely achieved using existing equipment.

Jan 1, 1983

By Ariti J

The mineralogy and extractive metallurgy of platinum and palladium in ores and residues is examined and the relative reactivity of Pt, Pd, PtS and PdS in cyanide and chloride media at 20¦C is discussed. Electrochemical measurements establish that Pd is readily leached in chloride media but more slowly in cyanide media due to a passivating PdO film. The passivating oxide film on Pt prevents leaching in either system at ambient temperatures. The results of leaching Au, Pd and Pt from an iron oxide residue obtained from the Sherritt Gordon Process using CN/air and Cl-/H202 are compared. It appears that passivation is overcome either by roasting at ?600¦ or by leaching at >_100¦C.

Jan 1, 1991

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

"In the UK, Ireland, and Western Europe, the mineral resource and reserve reporting standard is the PERC Code, developed and maintained by the Pan-European Reserves and Resources Reporting Committee, which is a standing committee set up under the auspices of a number of professional organisations which include the Institute of Materials, Minerals and Mining (loM3), the Geological Society of London (GSL), the European Federation of Geologists (EFG) and the Institute of Geologists of Ireland (IGI) to develop a Pan-European reporting code. The PERC Code supercedes the old IMMM Reporting Code 2001 and is recognised by the UK securities regulators and stock exchanges.""FOREWORD1 The Pan European Reserves and Resources Reporting Committee (PERC) Code for Reporting of Exploration Results, Mineral Resources and Mineral Reserves (further referred to as 'the Code') sets out minimum standards, recommendations and guidelines for Public Reporting of Exploration Results, Mineral Resources and Mineral Reserves in the United Kingdom, Ireland and Europe. The history of development of this code is summarised in Appendix 4.This 2008 edition supersedes all previous editions of The Reporting Code and the IMM Reporting Code.INTRODUCTION2 In this edition of the PERC Code, important terms and their definitions are highlighted in bold text. The guidelines are placed after the respective Code clauses using indented italics. They are intended to provide assistance and guidance to users in interpreting the application of the clauses in the Code. The same indented italics typeface formatting has been applied to Table 1, and to Appendices 1 and 2 which form part of the Guidelines.3 The Code has been adopted by the Institute of Materials, Minerals and Mining (loM3), the Geological Society of London (GSL), the European Federation of Geologists (EFG) and the Institute of Geologists of Ireland (IGI), and is therefore binding on their individual members.Appendix 1 contains a table of generic terms and their equivalents, designed to avoid unnecessary duplication or ambiguity in the textAppendix 2 provides Rules of Conduct for Mineral Resource and Mineral Reserve estimators that should be considered in addition to the Codes of Ethics normally applying to members of professional institutions."

Jan 1, 2003

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer' and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By N. F. Schulz, H. A. Lex, J. D. Zetterstrom

A green ball of iron ore faces many perils from the time it is formed until it finally emerges from the pelletizing furnace as a hardened pellet. For instance, if the rate of heat transfer into a ball is sufficient to produce vapor from either the free or combined water more rapidly than it can escape at a tolerable pressure, the ball may split, spall, or even explode, a failure commonly known as decrepitation. To avoid such failures, one must either limit the rate of heat transfer during the drying and preheating stages, at the expense of production rates, or improve the decrepitation resistance of the green balls. The latter remedy may often be accomplished through changes in ore preparation, balling procedures, or the judicious use of binders or other additives. INTRODUCTION Pelletization has become established as an especially desirable method for the agglomeration of fine taconite concentrates and it promises to be equally satisfactory for improving the physical structures of certain natural ores. A high-quality pelletized iron ore consists of uniformly sized spheres, usually about 1/2-in. diam, which are strong enough to resist abrasion and breakage during handling and which reduce well without disintegration in the blast furnace. The unfired agglomerates, "green balls", are subject to several destructive effects that must be avoided or minimized if a high-quality product is to be obtained by pelletization. Among these are abrasion and impact deformation or breakage during handling of the wet green balls, deformation and breakage by compressive forces in the bed of ore in the pel-letizing furnace, decrepitation during drying and preheating, wind erosion, and radial cracking at firing temperatures. Moisture condensation from the warm saturated gases downstream from the drying zone on wet, cool balls may cause bed collapse if it becomes excessive. Decrepitation is defined as the sudden disintegration of green balls, usually with an audible pop, that occurs when they are heated too rapidly during the drying or preheating stages of the pelletization process. The extent of ball disintegration may vary from merely splitting off a small fragment to almost total disintegration into the original ore particles making up the ball. Such ball destruction results in a decreased yield of pellets, and the fragments, which also tend to interfere by obstructing the gas flow through the bed, must eventually be screened from the fired product and recycled. The closely related type of ball failure that sometimes occurs during the high temperature firing stage, resulting in radial cracks without fragmentation, was not considered to be decrepitation for the purpose of this investigation. Failure by decrepitation is not usually a serious problem in the pelletization of taconite concentrates. The problem is significant, however, in the pelletization of some natural ores, especially those containing hydrous iron oxides. In some instances, economicd production rates cannot be maintained if the drying and preheating rates are slowed down enough to avoid decrepitation. OBJECTIVES This investigation was undertaken to: (1) Develop a practical laboratory means for quantitatively measuring the tendency for green balls to decrepitate in iron ore pelletizing furnaces, and (2) Investigate the causes and cures of ball decrepitation. MATERIALS Two iron ores were used in the work reported here: a taconite concentrate at 90% minus 325 mesh, containing 65.0% Fe, 8.4% SiO2, and no loss-on-ignition; and a crude oxidized ore at 54% minus 325 mesh, containing 59.1% Fe, 3.6% SiO2, 1.1% A12O3, and 9.5% loss-on-ignition. For a special test of effect of particle size distribution on decrepitation, two other

Jan 1, 1967

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By L. S. Darken, H. A. Wriedt

An investigation has been made of nitrogen absorption by the lattice defects in a low-carbon steel afte~ Plastic deformation. Specimens in which defects were distributed by various combinations of cold rolling and vacuum heat treatment were equilibrated with controlled ammonia + hydrogen mixtures at 300° to 450°C to study the relation between the solubility and the thermodynamic activity of nitrogen. The results are interpreted in terms of nitrogen being absorbed upon two different types of defect sites, called A sites and B sites. The concentrations of these sites are calculated for specimens with various histories of straining and annealing; and the thermodynamic relations descrihing the equilibrium distribution of nitrogen among the A, B, and ordinary interstitial sites in ferrite are evaluated as follows: THE generalization that the solute atoms in a solid solution interact with imperfections in the solvent lattice is now universally recognized and the subject of an extensive literature. All types of imperfections—point, line, or surface—exhibit these interactions, but the relative importance of each type depends upon its concentration, the strength of its interaction with the particular solute atom, and whether the interaction is attractive or repulsive. The strength and sign of the interaction vary with the vectorial displacement of the solute atom from the imperfection in the crystal. The concentration of lattice defects increases during plastic deformation and the effect of the imperfections upon the solute atoms is usually perceived only after cold work or irradiation. Two experimental methods have previously been used to observe the effects of interaction between nitrogen atoms and lattice imperfections in a iron. Internal friction, which was first used for this purpose by Dijkstra,1 has been applied more often than the electrical-resistivity method of Cottrell and Churchman.2 The method of the present investigation has not been used before.* Uniform specimens of steel with a metastable defect structure are produced by cold rolling and subsequent heat treatment below the recrystallization temperature. Variations in the defect structure are obtained by varying the amount of strain and the heat-treatment conditions. The specimens are then saturated with nitrogen at moderately elevated temperatures in ammonia + hydrogen mixtures having various thermodynamic activities of nitrogen below saturation with Fe4N. From the nitrogen contents of analyzed samples, the metastable equilibria of interactions between the defects and nitrogen can be established and the concentration of sites for nitrogen atoms in the lattice defects calculated. A steel was used in the present experiments instead of purified iron or iron alloys because the amount of nitrogen absorbed at defects is larger in the steel over a much wider range of experimental conditions and could therefore be measured more accurately. The effect of alloy composition is discussed in Part II of this paper; it is sufficient to say here that impurities and phase heterogeneity in ferritic alloys favor the generation and/or retention of larger defect concentrations during plastic deformation and annealing at 300° to 500°C. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental specimens were prepared from stock of a low-carbon steel, which will be called "X steel" here, with the composition: C, 0.12 pct; Mn, 0.43 pct; P, 0.010 pct; S, 0.034 pct; Si, 0.007 pct; As, 0.086 pct; Cu, 0.022 pct; Ni, 0.009 pct; Cr, 0.003 pct. The stock was all from a single ingot made by the basic open-hearth process, which was hot-rolled to strip 0.080 in. thick.. This hot-rolled strip, given the code designation "XH", was the starting material for preparing a series of cold-rolled sheets. The latter are designated "XC27",

Jan 1, 1965

By Martin Weinstein

A technique is described for preparing finegrained lead telluride by ultrasonic agitation of a solidifying melt. Material prepared by this technique is dense and chemically homogeneous. N-type PbTe, containing 0.03 mole pct PbIz, has been made and its thermoelecCric Properties have been measured as a function of temperature. For comparison, the properties of similarly doped PbTe made by cold pressing and sintering, and by extrusion, have also been measured. The ultrasonically prepared material compares favorably with the others in its thermoelectric-efficiency factor. Comparison of compressive-flow curves for the three kinds of PbTe show that the ulhasonically prepared material has much superior ductility. The cleavage strength of the ultrasonic material is related to the grain size, D, by the Petch relation:Extrapolation to infinite grain diameter yields a fracture strength of 5000 psi for single-crystal PbTe. WHEN metals and semiconductors solidify in a mold they normally assume one of three cast structures illustrated in Fig. 1.' Solidification in a casting starts at the mold walls where a large number of fine crystals of random orientation can be nucleated to form the chill zone. Because of the anisot-ropy of the growth rate, those crystals whose direction of maximum linear growth is parallel to that of the heat flow grow faster and crowd out the crystals of less favorable orientation. A second zone, having a preferred orientation, called the columnar zone, thus forms adjacent to the chill zone. The speed of growth of the columnar grains will depend, in the case of limited undercooling of the melt, on the rate at which heat can be abstracted. The columnar zone can extend to the center of the casting, Fig. l(a), but it is frequently followed, in solid-solution alloys, by another zone of equiaxed randomly oriented grains in the central portion of the casting, Fig. l(b). The equiaxed structure in Fig. l(c) represents the completely grain-refined case where the equiaxed grain size is small. The third type of structure is the most desirable because it imparts a somewhat higher strength for all except high-temperature applications, it reduces segregation of the doping constituent, and it reduces the possibility of hot tearing (the separation of grains due to the melting of a low-melting point constituent in the grain boundaries). In order to obtain fine-grained castings, the nu-cleation frequency must be increased and grain growth must be restricted. Various techniques have been employed for obtaining this end, namely: rapid cooling, vibration, and inoculation of the melt. The success of these techniques depends upon the characteristics of the metal species and on factors controlled by heat transfer through the crucible walls. Recent studies2" have shown that the application of ultrasonic energy to the solidifying ingot is an extremely powerful tool in the improvement of the crystalline structure of metallic castings. Both the mechanical properties and homogeneity of the ingots are improved. Ultrasonic oscillations may affect the crystallization process by 1) permitting subcritical nuclei to agglomerate and thus form nuclei of sufficient size to cause crystallization, 2) changing the state of surface adsorption of various catalysts found in the liquid melt, 3) breaking pieces of solid from the solidified surface near the supercooled region thereby increasing the number of possible nuclei, 4) causing temperature fluctuations to occur in certain parts of the melt thereby increasing the supercooling at specific points in the liquid, and 5) decreasing the critical nucleus size by increasing the pressure at specific points in the melt.' Various investigators have concluded that the effectiveness of the ultrasonic oscillations results from cavitation which disrupts the growing solid-liquid interface The present paper describes the application of ultrasonic oscillations to the crystallization of the semiconductor N-type PbTe. The purpose of this study is to prepare crystalline

Jan 1, 1964

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970