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By T. Weatherwax

As part of a strategic research initiative at UBC to design and evaluate integrated underground mining and mineral processing systems, work has been done to determine how to utilize the coarse rejects of pre-concentration in the underground environment. An amenability study for nine orebodies from four of Xstrata Nickel?s Ontario operations evaluated both processing and waste disposal methods. The utilization of the rejects as a high quality backfill with minimal binder requirements has been identified as the preferred disposal method. Fill mixes utilizing the rejects in combination with classified tailings, full tailings, and cement were developed based on the geotechnical properties of the rejects. The mix designs were examined for both strength and rheological properties. The paper will present the results of the pre-concentration testwork, the design and strength testing of various mix designs for rejects from the nine ores and presents a conceptual design for an underground pre-concentration system based on this test work.

Jan 1, 2008

By Joseph L. Young, Richard A. Bohling

To keep Homestake's Bulldog Mountain silver and lead mining and milling operation in southwestern Colorado workable, natural ground water and decant water from the mine's sand backfilling operation must be continually pumped from the workings. Left untreated, this water exceeds maximum allowable levels for various contaminants that may be discharged to the environment. To comply with regulations, a National Pollutant Discharge Elimination System (NPDES) permit was obtained and a mine water treatment plant for heavy metals removal was constructed in 1977. Due to equipment capacity and operational problems, and the lack of on-site technical personnel and analytic equipment, the first water treatment plant could not consistently meet permit limits. In 1979, Homestake entered into a consent decree with EPA and the Colorado Department of Health, calling for the construction of a water treatment facility to meet NPDES permit limits. Initial construction began in the spring of 1980 and the plant now produces effluent acceptable for discharge.

Jan 12, 1981

By R. L. Virta

Twenty-three companies mined kaolin in nine States in 2004. Production was estimated to be 7.6 Mt (8.3 million st) valued at $912 million, based on preliminary data. This was a slight decrease from 7.68 Mt (8.46 million st) valued at $939 million in 2003.Georgia was the leading producer state with an estimated 6.5 Mt (7.1 million st) in production. It was followed, in decreasing order of tonnage, by South Carolina, Alabama, California, Texas, Arkansas, Nevada, Florida and North Carolina. Georgia accounted for nearly the entire domestic water-washed, delaminated, and pigment-grade calcined kaolin production. Consumption Sales to the paper industry accounted for 49 percent of domestic sales and 64 percent of total sales. Other major markets for domestic sales were refractory products (10 percent), paint (5 percent), fiberglass (4 percent), catalysts (3 percent) and rubber (2 percent).Paper coating and filler markets accounted for about 87percent of export sales of kaolin.

Jan 1, 2005

The inquiry into the explosion at the Moura No. 2 Mine in August 1994 recommended -?Emergency procedures should be exercised at each mine on a systematic basis, the minimum requirement being on an annual basis for each mine.? (Windridge et al. 1996). In December 1996 the ?Approved Standard for the Conduct of Emergency Procedures Exercises? was published and has been subsequently revised (Queensland Department of Mines and Energy Safety and Health Division 1999). This document provided guidelines for conducting mine site emergency exercises as well as the requirement for a test of state-wide emergency response by holding a Level 1 Mine Emergency Exercise at one mine on an annual basis. From 1998 to date (January 2008) ten Level 1 Mine Emergency Exercises have been held in Queensland, Australia. This paper discusses each of the exercises conducted to date as well as the logistics, scenario preparation, planning and organising required to conduct emergency exercises at this level.

Jan 1, 2009

By Martin Stoklossa

Surface mining operations typically require run-of-mine material to be sized for further processing. In-pit crushing facilities serve this need, as stationary, semi-mobile or fully mobile units. Although in particular fully mobile crushing facilities have been in use for over half of a century, other surface mining techniques have typically been implemented. However, with increasing operating costs in truck and shovel operations, and other economic considerations, mobile crushing plants are increasingly a viable option. The operational and economical parameters in relation to the optimal surface mining equipment selection will be reviewed. The role of the mobile crushing technology within the continuous vs. noncontinuous surface mining operation and basis for mine planning are also discussed. Current applications and respective case studies will be reviewed. Key performance indicators will be presented. These performance parameters can be viewed as a tool to aid in the equipment selection process. The future direction for further research and development in mobile crushing facilities will also be presented.

May 1, 2008

By M. Görnerup, A. Kapilashrami, Seetharaman. S., A. K. Lahiri

Simultaneous reduction and foaming of chromium-rich slag have been studied in a laboratory furnace equipped with X-ray image analysis. Reduction of the metal oxides by graphite generated CO, which caused the melt to foam. The slag composition continuously changed due to reactions and dissolution of lining. Gas generation rate, foam height, and gas bubble size were studied and correlated to slag composition. Viscosity increased significantly during the experiments due to a change in slag composition. Bubble sizes varied little during the progress of reactions but differed considerably for different slags. Bubble sizes were largest for V2O5 containing slag, which is contrary to the general understanding that the presence of strong surface active agents reduces the bubble size. The foaming index did not follow expected trends for bubble size and viscosity, suggesting that foaming index is not a suitable parameter for discussion of foams under dynamic conditions. Keywords: slag, foaming, dynamic conditions

Jan 1, 2004

By Liming Yuan, John C. Edwards, Gene F. Friel, Robert A. Franks

Diesel fuel fire experiments were conducted in NIOSH’s Pittsburgh Research Laboratory’s (PRL) Safety Research Coal Mine (SRCM) to determine the critical air velocity for preventing smoke rollback. Such information is necessary for the preplanning and implementation of ventilation changes during mine fire fighting and rescue operations. The fire intensity varied from 50 kW to 300 kW depending upon the fuel tray area. Airflow in the 2 m high and 2.9 m wide coal mine entry was regulated during the course of each experiment; measured upwind from the fire as an average over the entry cross-section with an ultrasonic airflow sensor; and recorded dynamically with a mine monitoring system. The extent of smoke reversal was monitored with light obscuration monitors, ionization smoke sensors, and visual observations. Experimental results for the critical air velocity for smoke reversal as a function of fire intensity compared very well with model predictions based upon a computational fluid dynamics (CFD) fire dynamics simulator.

By Liming Yuan, John C. Edwards, Gene F. Friel, Robert A. Franks

Diesel fuel fire experiments were conducted in NIOSH’s Pittsburgh Research Laboratory’s (PRL) Safety Research Coal Mine (SRCM) to determine the critical air velocity for preventing smoke rollback. Such information is necessary for the preplanning and implementation of ventilation changes during mine fire fighting and rescue operations. The fire intensity varied from 50 kW to 300 kW depending upon the fuel tray area. Airflow in the 2 m high and 2.9 m wide coal mine entry was regulated during the course of each experiment; measured upwind from the fire as an average over the entry cross-section with an ultrasonic airflow sensor; and recorded dynamically with a mine monitoring system. The extent of smoke reversal was monitored with light obscuration monitors, ionization smoke sensors, and visual observations. Experimental results for the critical air velocity for smoke reversal as a function of fire intensity compared very well with model predictions based upon a computational fluid dynamics (CFD) fire dynamics simulator.

Jan 1, 2005

By Ali Kahriman, Alper Celtikc, Serdar Celik, Tuncer Gungor

This paper presents the results of ground vibration measurements carried out in Gülyali Hisarcik Basalt open pit mine located on the north side of the Anatolia near Ordu province in Turkey. Within the scope of this study in order to predict peak particle velocity level for this site, ground vibration components were measured for 5 shots during bench blasting. In blasting operations; ANFO (blasting agent), gelatin dynamite (priming) and delay electric detonators (firing) were used as explosives. Parameters of scaled distance (charge quantity per delay and the distance between the source and the station) were recorded carefully and the ground vibration components were measured for all blast events using 5 different vibration monitors (4 White Mini-Seis and 1 Instantel Minimate Plus Models). The absolute distances between shot points and monitor stations were determined using GPS. The equation of square root scaled distance extensively used in the literature was taken into consideration for the prediction of peak particle velocity.

Jan 1, 2013

By R. Bauer

Adaptations and redesign of the existing already very successful and proven road milling machine concept and technical innovations such as an optimized, specifically for mining application developed cutting drum, cutting housing design and cutting tools, high manoeuvrability achieved via a tight turning radius, a three disk clutch system and a cutting drum drive that allows for the acceptance of higher loads, a complete reinforcement of the chassis to withstand higher vibrations and torque, the installation of increased engine power via a modern drive unit, a specifically for mining/construction applications developed operator’s platform and finally a redesigned air intake system and the adaptation of the levelling system resulted in far more cost effective and advantageous capabilities of Wirtgen Surface Miner in soft to medium hard mining and construction applications. As the achieved results show for the first time in modern surface mining history mechanized cutting is capable to compete successfully against traditional drill, blast/ripping and other conventional mining methods.

Jan 1, 2007

By A. Hotta

Reduction of CO2 emissions is the key driving force behind the development and implementation of new solutions for energy production. One solution is circulating fluidized bed (CFB) combustion technology combined with a high-efficiency once-through water-steam cycle. Foster Wheeler's CFB technology is today commercially available in capacities up to 800 MWe with ultra-supercritical steam parameters. Simultaneously, the Flexi-Burn® CFB technology is being developed to provide capability of flexible operation in air firing and oxy-combustion for carbon capture. CFB technology can offer an attractive solution for the reduction of CO2 emissions, owing to advantages such as fuel flexibility and low emissions that the air-fired CFB technology offers today. Pilot test facilities provide information about the performance of CFB oxy-combustion technology, and the acquired knowledge is being incorporated in boiler modelling and design tools. One of the European R&D initiatives on carbon capture and storage (CCS) is the Technological Centre for CO2 Capture and Transport, which is supported by the Spanish Government through the Fundación Ciudad de la Energía (CIUDEN). CIUDEN is a research and development institution created by the Spanish administration in 2006 and fully conceived for collaborative research in CO2 capture, transportation, and storage. The Technology Development Centre for CO2 Capture and Transport comprises two technologies on oxy-combustion: pulverized coal (PC) and circulating fluidized bed (CFB). This paper will focus on the design and main characteristics of the 30 megawatt-hour thermal capacity (MWth) oxy-CFB boiler. Foster Wheeler is the technology provider of the Flexi-Burn CFB unit, for which commissioning has been completed in the first quarter of 2011. The CFB unit design allows operation either under conven¬tional combustion with air or under oxy-fuel conditions. The size of this experimental boiler is sufficient to allow the scaling of the results to commercial units. In this way, multiple fuels and operating conditions can be tested economically. The results will validate the design of a future 330 MWe supercritical Oxy-Combustion Power Station (OXY-CFB-300 Compostilla Project) intended to demonstrate the CCS technology at commercial scale. The Compostilla OXY-CFB-300 Project is one of the six CCS demonstration projects funded under the European Energy Programme for Recovery (EEPR) of the EU. The project is based on a future 330 MWe CFB supercritical oxy-combustion plant, with CO2 storage in a deep geological formation. The first phase of the project, granted by the EEPR programme and led by the Spanish utility ENDESA, includes all studies and characterization work needed on CO2 capture, transport, and storage, as well the costs, financing, and regulatory and permitting required, prior to the final investment decision for the construction phase of the plant by the end of 2012.

Jan 1, 2012

By Donald J. Murphy

Longevity of structural units, as compared to the planned useful life of a facility, always is a design consideration. Typical concerns include slow decay due to environmental factors, and changes in constitutive relationships governing the performance of the material involved. With respect to foundations, the usual items of interest are corrosion of steel and concrete, and time dependent behavior of the soil/structure system. For piles, as with other foundations, deterioration is precluded, mitigated or otherwise accounted for by assessing properly the ambient situation (sulphates, pH, stray currents, resistivity) and providing safeguards, such as resistant construction products, oversizing, coatings, and/or cathodic protection. On the other hand, long term performance of the pile foundations, as affected by time dependent characteristics of the supporting soil or rock, can be predicted and controlled only with a synergetic coupling of analyses and field tests. The history of a project for which this approach was followed forms the basis for this paper.

Jan 1, 1986

By Jeffrey L. Pagnutti

Train derailment can lead to loss of capital, damage to the environment, and loss of life. Machinery condition monitoring techniques can be used to develop a structural health monitoring system for railway track to detect faults at the incipient stage, before catastrophic failure occurs. This study uses vibration measurements from a novel material haulage unit to develop a decision support system for railway track maintenance. A variety of feature sets and classifiers were compared to determine the optimal configuration for fault detection. The results highlight the shortcomings and advantages of certain methods and describe the process in which the optimal result was obtained. The Parzen data descriptor paired with a refined statistical feature set performed the task of fault detection with less than five percent false positive and false negative classification error. Overall, the outcome of these experiments indicated that condition monitoring of railway systems is a promising approach for fault detection and has the potential to avoid catastrophic failure.

May 1, 2013

By H. V. Welch

In this paper, as prepared for delivery at the Southern California regional meeting on Oct. 14, 1948, it was thought best to interpret the term "economics" in a rather broad manner and to include, in addition to the material losses and recoveries and associated monetary values (Part I), a limited discussion of the increased difficulties or the particular problem and the special requirements, as the particle sizes of the suspended particles range down from the relatively coarse to 100, to 10, to 1 micron or even to a fraction of one micron (Part II). Further, it is not quite in order to overlook entirely the community and individual health problems, although space requires the economics of this to be considered only very incompletely. Therefore, Part III, covering this phase of the subject, is very limited. This paper, then, is divided into 5 parts or headings as follows: I Losses and/or values in suspended solids. II Particle size. III Dust and fumes in community and individual living. IV Means and Procedures for dust and fume collection. V Description or examples of specific equipment in service and of the several types used for dust and fume collection. Because of the wide extent and wealth of subject material available and the space and time limitation imposed, presentation and discussion are less than originally planned. I—Losses and/or Values in Suspended Solids The weight involved in moving streams of industrial plant gases is commonly not appreciated, neither is their carrying power in the weight of solids maintained in suspension and moved with the gas stream from a point of origin or pick-up to a point of dissipation or settlement. These, however, are major weight figures; for example, in a modern iron blast furnace there may be five tons of gas for every ton of iron produced and by the time this blast furnace gas has been burned in stoves or under boilers the weight of gas discharged to atmosphere is on the order of eight times the weight of iron produced. Similarly for nonferrous metallurgy there may readily be from 10 to 20 times the weight of gases discharged to atmosphere as there is metal produced. A cement kiln in operation or a kiln in service to produce metallurgical lime may have on the order of 5 to 6 times the weight of stack gases as of clinker or lime produced, and at least the cement kiln, because of the very fine nature of its feed, is a very heavy dust producer. It may be noted that there have been two developments in progress for nearly three decades. Both are extraordinary in the industrial economics effected and in their ready availability to ever larger units of operation and their ever widening importance in industry, and both are productive of great quantities of finely divided material in furnacing. The first of these is the flotation process for ores, especially the metallics such as copper, lead, and zinc; and the second, powdered fuel combustion for power plant, industrial plants and metallurgical operations. Today, new developments, for example, flotation for the nonmetallics such as higher grade limestone for cement manufacture which requires still finer grinding and the powdered-coal-fired boilers with production ratings of over 1,000,000 lb of steam per hr, bring still more concentrated and hugely increased quantities of stack emission. Perhaps the honors for the greatest interest in the quantities and values escaping in waste furnace and equipment gases belong to the nonferrous metallurgical operations. Their record of achievement in the installation of dust and fume collection equipment, largely baghouses or Cottrell electrical precipitators, is exceeded by no other industry. Something of the magnitude and variety of equipment utilized in such recovery systems was covered by the writer in two papers presented to the Institute some 10 years ago.1,2 It is not intended to repeat the material of those articles, but it is thought that they complement this offering and should be noted. COPPER ROASTERS As the copper roasters are the first of the series of furnaces handling the copper-bearing concentrates in the usual copper smelter of today, it is in order to make them the first consideration. Multiple hearth sulphide roasters, not hard driven, often maintain their dust loss through exit gases at 3 pet or below of feed to furnace; in hard-driven or maximum-driven furnaces, exit gas losses often approximate 7 pet of charge with a ±2 pet variation for special conditions prevailing at some plants. A 5 pet loss of feed in a roaster gas exit, unless reclaimed, often makes the difference between a profit and loss operation, and in many cases substantial recovery is the very basis of dividend payments. As there is available very practical and successful equipment for the collection of the

Jan 1, 1950

By Benny J. Nelson

AS a part of the fundamental research program of Aluminum Research Laboratories, some data were obtained on the ternary system Mg-Al-Mn. As very little information on the magnesium corner of this diagram has heretofore been published, it seems desirable to make available the values found for the liquidus and solidus surfaces of this system. Procedure The settling procedure was used for the determination of the liquidus compositions. Metallo-graphic examination of quenched samples, and stress-rupture upon incipient melting, were used for the solidus determinations. The settling procedure has been described in a previous paper.' Briefly, this method involved saturating the alloy with manganese at a temperature substantially above that at which the sohbility was to be determined, then cooling the melt to the latter temperature, and holding it at that temperature for a substantial period of time. Samples for analysis .were carefully ladled from the upper portion of the melt at hourly intervals during the holding period. After the ladling of each sample, the melt was stirred to redistribute some of the manganese that had already settled, because it appeared that when the latter particles of manganese again settled, they aided in carrying down more of the manganese and thus hastened the attainment of equilibrium. The melts were prepared and held in a No. 8 Tercod crucible holding approximately 4 lb of metal. The manganese was added either in the form of a prealloyed ingot (Dow M) containing about 1.5 pct Mn or by the use of a flux (Dow 250) containing manganese chloride. In calculating the flux additions, it was assumed that the manganese introduced would be equal to 22 pct of the total weight of the flux. Temperatures were measured with an iron-constantan thermocouple enclosed in a seamless steel tube, the lower end of which was welded shut. This protection tube also served as a stirring rod. The samples ladled from the upper portions of the melts at the various intervals were analyzed for aluminum, manganese, and iron. When making the alloys which were to be used for the determination of the solidus, 2½ in. diam tilt mold ingots were cast, scalped to 2.0 in. in diam, and extruded into ? in. diam wire. The principal impurities in the melts for this investigation were iron and silicon; their total not exceeding 0.03 pct. Portions of the wire, approximately 2 in. in length, were enclosed in stainless steel capsules for protection from the atmosphere. Bundles of these capsules, with a dummy capsule containing an iron-constantan thermocouple, were heated inside a large steel block (acting as a heat reservoir) in a closed circulating-air type electric furnace. At ap- propriate times, the capsules were removed and quenched in water. The wires were examined metallographically to determine the temperature of initial melting. Short times at temperature were used at the beginning for wire specimens of all alloys to obtain quickly the approximate temperatures at which melting could be first observed. When approximate solidus temperatures had thus been determined, equilibrium heating was attempted. This equilibrium heating consisted of an 8 or 16 hr period at a temperature, about 50 °F below the lowest temperature at which melting occurred when short heating cycles were used, followed by further heating for 1 hr periods at consecutive 10" higher temperatures. The theory for the method of stress-rupture at incipient melting has been well covereda and its limitations are recognized. Thus, if the interfacial tensions are such that the first minute quantity of liquid is "bunched up" at the grain boundary junctions instead of spreading out along the grain boundaries,³ temperatures higher than the solidus are required before melting will be manifested by rupture of the specimen. This point will be elaborated later. Specimens of the wires with a reduced section (approximately 1/16 in. diam) were suspended vertically in a tubular furnace. The setup used is shown in Fig. 1. The clamp holding the specimen was made from alumel thermocouple wire and the thermocouple was thus completed across the specimen by attaching a chrome1 wire to its lower end. Temperatures were read from a Speedomax recorder used in conjunction with a calibrated thermocouple. The small weight attached to the specimen and a vibrator attached to the furnace tube, to aid in distributing the molten constituent along the grain boundaries, were used to bring about rupture at a temperature closely approximating the solidus. The specimens were heated at a rate of about 5°C per min. The rupture of the specimens was indicated both by sound and by the action of the recorder. An argon atmosphere containing a small amount of SO² was used for protection of the specimen. The assembly was taken out of the furnace immediately following rupture and the specimen removed. Some of the broken specimens were examined metallographically and will be referred to later. Results and Discussion Fig. 2 shows a set of typical time-composition curves for liquid samples of the Mg-Al-Mn alloys used for the settling tests. The data as presented

Jan 1, 1952

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.' It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)'/2af.]' [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By E. C. W. Perryman

The recovery and recrystallization characteristics of superpurity aluminum have been investigated using electrical resistivity, X-ray line breadth, and hardness measurements for the former and the micrographic method for the latter. The three different properties recover at different rates and have different activation energies. The recrystallization results agree well with Avrami&apos;s theory and furthermore indicate that the perfect subgrains formed during recovery are not the nuclei for re-crystallization. WHEN a metal is plastically deformed, its physical and mechanical properties generally undergo considerable changes and by subsequent annealing these changes are partly or wholly annihilated. Thus, a recovery process can be discussed, taking this term in its general sense. In practice, however, there is reason to discriminate between two apparently different processes, one most easily followed at low temperatures, in which the properties return to an almost constant value between that of the cold worked and fully annealed material, and a second process in which the properties return to their original values before cold working and which is accompanied by the formation and growth of new grains having an orientation different from that of the matrix. In this paper the word recovery will be taken to mean the changes in some property as a function of annealing time which occur either without the appearance of new grains or under conditions such that the new re-crystallized grains are very small (= 2 microns), are very few in number, and substantially do not affect the property being measured. This definition is rather abitrary, for it will depend upon the sensitivity of the technique used for the observation of new recrystallized grains, which in the present work was about 1 to 2 microns. However, it is helpful to use the term recovery in this sense and to reserve the term recrystallization for the processes of nucle-ation and growth of new grains in the cold worked matrix. Although considerable work has been done on recovery and recrystallization, most workers have based their study on the measurement of one or perhaps two parameters. Since very small amounts of impurities have such a profound effect on the recrystallization characteristics of a pure metal, it becomes extremely difficult to correlate one piece of work with another. With this in mind, the present work on recovery and recrystallization was done on the same material. Experimental Procedure Material Used and Fabrication: The composition of the superpurity aluminum used throughout this investigation was 0.002 pct Cu, 0.003 pct Fe, 0.003 pct Si, and <0.001 pct Mg. The ingot was hot rolled to 0.250 in., annealed, and cold rolled to 0.034 in. A large number of reductions and intermediate anneals were carried out so as to produce material with a minimum of preferred orientation and maximum homogeneity. For the recovery part of the investigation, the final cold reduction was 20 and 80 pct and for the recrystallization part, 20 pct. After each pass in the cold rolling process, the material was quenched in cold water in order to keep the rolling temperature as near room temperature as possible. Annealing Procedure: For the recrystallization work, specimens 1x1 in. were cut from the 0.034 in. cold rolled sheet and a hole was drilled in each through which a wire was threaded to support it in the salt bath. The temperature of the salt bath was controlled to +2°C and the time taken for a specimen to reach temperature was approximately 5 sec. These 1 in. squares were then divided into three groups, one of which was given 5 min at 318°C and another 2 hr at 244°C. These treatments were such that recovery was almost complete and a well defined subgrain structure produced. Separate specimens of each group were annealed for different times at 301°, 318°, 355°, and 373°C, i.e., three specimens for each annealing time. The delay between finish of cold working and start of annealing was about 1 hr. For the recovery work, strips 0.062 in. thick were cut from the cold worked sheet, annealed, and then given the last cold rolling operation. This was done for each annealing temperature. By this means it was possible to minimize the delay between cold working and annealing. In general, all measurements were carried out within 1 hr of the last cold rolling operation. Annealing at low temperatures was done in an oil bath the temperature of which was maintained constant to +1°C. Electrical Resistivity Measurements: Strips 20x0.5x0.05 in. were machined and the electrical resistance measured using a Kelvin double bridge. Measurements were made in an oil bath maintained at 20rt0.1°C. The same specimen was used for the complete isothermal annealing curve.

Jan 1, 1956

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970