Search Documents

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine&apos; who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H&apos;-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson&apos;28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By H. Rumfelt

The author demonstrates an approach for analyzing overcasting requirements for a stripping project. This approach to the problem employs indicated trends in the relationship of the weight of the machine (only electropowered draglines are considered) to its ability to do stripping work. Strip mining in the domestic coal industry is contributing a greater proportion of overall production than at any time in the past. U.S. Bureau of Mines statistics show that the percentage of total production mined in 1958 by stripping methods increased to more than 30 pct, up from 22 pct in 1951. The tendency to favor strip and open pit mining exists in other mining activities, but such trends are not as clearly outlined as in the coal industry. Significantly, the depth of overburden in coal properties considered suitable for stripping is also increasing. A depth of 50 to 60 ft of overburden was once considered to be about the maximum amount that could be handled economically. Today, a depth of 80 to 100 ft is frequently taken into consideration for simple overcasting operations (i.e., excavating overburden and dumping it in the spoil position where it remains indefinitely). Accompanying these changes, there have been continuing studies searching for procedures to appraise deeper stripping problems. Although the only known practicable way to accurately evaluate a proposed stripping venture is to make studies (including cost estimates) step by step, it is nevertheless desirable to have a quick method for making preliminary evaluations of potential strip mining operations. A recently devised digital computer method of providing a preliminary simple overcasting analysis for a stripping prospect relates the indicated trends in the relationship of the weight of the machine to its ability to do stripping work. In addition, this approach employs situations where the geometry of each cut-and-spoil section is assumed to take certain defined relationships for varying overburden depths. Slopes are necessarily considered to be stable, which means such practical factors as the mechanics of soils are neglected for the sake of convenience. Definition of Terms: Photographs A and B show a shovel-type and a dragline-type of simple overcast operation, plus terms used to denote certain parts of a pit. Pits that follow a straight line when projected on a horizontal plane are referred to as straightaway. It has been assumed that all section drawings accompanying this article pertain to straightaway cuts which, in turn, means that areas can be compared by relative volume. The volume of overburden is measured in virgin cubic yards. Material displaced from its virgin state to a spoil area normally occupies a larger volume than when in situ; the difference is termed swell, and it is expressed as a percentage of the original volume. For example, if the original cut volume is denoted V cu yd, and the spoil volume is 1.2 V cu yd, the swell is a positive 20 pct. MAXIMUM USEFULNESS FACTOR (MUF) CONCEPT Men experienced in overburden removal give emphasis to the weight of the machine in relation to its value as an excavator. From the writer&apos;s understanding, value has been only loosely defined and discussed generally and vaguely. The concept is considered important, however, since it is based upon the observations of many men. It provides a clue for the approach taken to solve deep stripping problems. In the procedure described below, value has been arbitrarily established as the product of the nominal dipper size of the shovel (or dragline) times a functional dumping reach. MUFs—Shovel: A shovel&apos;s capability to handle thick overburden is usually limited by its ability to dispose of the spoil. Thus the dumping reach, as well as its dumping height, is significant. The angle of repose of spoil material must also be considered. Although such slope angles vary among different mines, jobs, and materials, a slope of 1.25 to 1, frequently found in both planning and practice, is used by this author in the illustration of this analytical method. The relationship of the shovel&apos;s geometry to a stripping operation is shown in Fig. 1. To gain maximum advantage in constructing spoil piles, the shovel is placed so that its tracks adjacent to the spoil are as close as possible to the rib of the coal deposit. A vertical plane passing through the line

Jan 1, 1961

By Leon Eliel

TEN years ago a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these isolated bits of infor-mation can be ascertained, the message begins to take meaning. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of, a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern .he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

By William E. Ford, Edward Salisbury Dana

1. Normal Class (31) Axinite Type 2. Asymmetric Class (32) Calcium Thiosulphate Type Mathematical Relations of the Triclinic System 216. Crystallographic Axes. - The triclinic system includes all the forms which are referred to three unequal axes. with all their intersections oblique. When orientated in the customary manner one axis has a vertical posi-

Jan 1, 1922

By F. Milton Lewis, James L. Coburn

In this paper the economics for a conventional comminution system, consisting of three stage crushing and one stage ball mill grinding, are compared to a semi-autogenous/ball mill comminution system. Capital and operating costs for a copper concentrator in Arizona at two levels of production, 20 and 40 thousand short tons of ore per day, are estimated. In order to minimize the investment and operating costs, large size equipment is selected for all four cases. These cost data are evaluated and conclusions are presented.

Jan 1, 1982

Jan 1, 1933

By Norman P. Goss

It is generally agreed that cold-working mechanically refines the grains into smaller fragments and with continued working these are oriented with certain crystallographic directions bearing a relation to the direction in which the metal is worked. Some of the energy expended on the metal during plastic deformation appears in the form of heat, but a very small portion remains in the metal as stored energy. The entropy, specific heat capacity, temperature at which recrystallization will just begin, density, ductility, elasticity, tensile strength, and resistance to corrosion are affected. These properties have been studied extensively and some of the changes in the physical properties due to cold-working were attributed to lattice distortion.l-8 The broadening of the Ka lines on the X-ray diffraction diagrams of plastically deformed metals is believed to indicate lattice distortion, and consequently the existence of internal stresses. The evidence supporting this theory rests solely upon the observed experimental fact that the diffraction lines are broadened and the Ka doublets are completely diffused. Elam9 has reviewed the matter of lattice distortion in relationship to the hardening of metals by plastic deformation. The X-ray diagrams of plastically deformed metals differ in general from annealed metals. The hardening of a metal was believed due to lattice distortion.9 The resolution of the doublet is lost when a metal is cold-worked and the Laue spots are elongated. At one time this elongation was thought to indicate the elastic bending of the crystal planes. However, more careful work showed that the asterism was due to new orientations developed within the fragmented grains during plastic deformation. Some theories attributed the hardening to fragmentation of the grains into smaller units. Jeffries and Archer,ll after carefully considering the problem of work-hardening from many angles, came to the conclusion that cold-working mechanically refines the grains into smaller crystal fragments, some of which at least differ in orientation from the parent grain. The increase in

Jan 1, 1940

By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By D. A. Dahlstrom

WITHIN the past decade, certain economic, legal, and technological changes have intensified the necessity for an efficient classifier or deslimer of particles at and below the 200-mesh point. First, mechanization of mining has increased the percentage of clays, silts, refuse, and high-ash material in the run-of-mine coal. Second, many washing plants must rely on smaller percentages of fresh make-up water because of shortages, economic factors, or legal restrictions on waste water disposal. Finally, the crushing of middlings and coarse refuse plus the trends toward the finer sizes in sales has further increased the amount of fines produced per ton of mine-run coal. A joint consequence of these circumstances has been the augmented percentage and build-up of —200-mesh material in the finer coal fractions and tipple circulating water. This results in the following disadvantages to the operator: (1) Higher ash percentages in the fine coal caused in large measure by the greater ash content of the —200-mesh material, (2) more difficult or expensive recovery of the fine coal from plant slurries, (3) lower filtration, drainage, and drying rates caused chiefly by lower permeability and the greater surface exposed per unit mass of the finer particles, (4) greater difficulty of beneficiatiing the fine coal because of lowered equipment efficiency and the partial "coating-out" of the —200-mesh fraction on the coarser coal particles. Obviously some cheap but effective fine-size classifier must be developed to aid in solving the above problems. To eliminate the generally unwanted —200-mesh fraction from coal slurries, several methods are in use. Probably the most popular with coal operators is the settling cone wherein the larger particles settle downward to the apex of an inverted cone while the slimes and fines are carried upward by vertical fluid currents caused by the overflow of the bulk of the water at the outer rim. The main advantage of the unit is the low initial and operating cost since no moving parts are involved. Disadvantages are primarily low capacity per square foot or floor space and the loss of good coal in the overflow above the 100-mesh size due to localized, high-velocity gradients and nonuniform, fluid-flow patterns, especially at high loadings. Also, when high slime concentrations are present, desliming efficiency is severely injured.&apos;, &apos; Other methods employed are the drag and spiral classifiers and the hydroseparator.&apos; These involve mechanical separations achieved by moving parts and naturally result in higher initial costs. As they are all based on the settling velocity of the particles at the mesh of separation under operating conditions, area requirements are again large per gallon of throughput if they are to classify at the 200-mesh point. Usually the selection is made to operate at a higher throughput and thus sacrifice some coarser coal in the slime overflow. Cyclone Possibilities in Desliming To overcome the disadvantages of present deslirning methods, it is necessary to use a device that exhibits a very stable and uniform flow pattern while greatly increasing the settling velocity of

Jan 1, 1952

By T. Egleston

The importance of condensing the gases which escape from furnaces so as to save both the fine particles of ore carried off mechanically and those which are volatilized, has for a long time occupied the serious attention of metallurgists in all parts of the world. It was my good fortune during the last summer to visit the lead and silver works at Ems, near Coblentz on the Rhine, and through the politeness of Mr. Freudenberg, general director of the works, to study in detail their methods of condensation, and to receive from him the important results which have been obtained through a series of experiments lasting over a number of years. I have thought, that these results would be of great interest to the members of the Institute and to other metallurgists in the United States, and I have, therefore, with the assistance of Mr. Freudenberg, prepared a careful, detailed description of the construction of the flues, as well as an account of the various experiments which have been made with them, and the conclusions arrived at as the result of these experiments. It may be said, in general, that the reason why so little attention has been paid in the metallurgical works of the United States to the collection of flue-dust, is that we are not generally aware of the large amount of material carried off by the gases. This is owing partly to the fact that little or no attention is paid to the subject, and also to the fact that the assays, which are almost invariably made in the dry way, show a result so much below the real contents

Jan 1, 1883

By P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.&apos;&apos;&apos; A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.&apos; In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.&apos;&apos;7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961

By Norman P. Goss

It is generally agreed that cold-working mechanically refines the grains into smaller fragments and with continued working these are oriented with certain crystallographic directions bearing a relation to the direction in which the metal is worked. Some of the energy expended on the metal during plastic deformation appears in the form of heat, but a very small portion remains in the metal as stored energy. The entropy, specific heat capacity, temperature at which recrystallization will just begin, density, ductility, elasticity, tensile strength, and resistance to corrosion are affected. These properties have been studied extensively and some of the changes in the physical properties due to cold-working were attributed to lattice distortion.l-8 The broadening of the Ka lines on the X-ray diffraction diagrams of plastically deformed metals is believed to indicate lattice distortion, and consequently the existence of internal stresses. The evidence supporting this theory rests solely upon the observed experimental fact that the diffraction lines are broadened and the Ka doublets are completely diffused. Elam9 has reviewed the matter of lattice distortion in relationship to the hardening of metals by plastic deformation. The X-ray diagrams of plastically deformed metals differ in general from annealed metals. The hardening of a metal was believed due to lattice distortion.9 The resolution of the doublet is lost when a metal is cold-worked and the Laue spots are elongated. At one time this elongation was thought to indicate the elastic bending of the crystal planes. However, more careful work showed that the asterism was due to new orientations developed within the fragmented grains during plastic deformation. Some theories attributed the hardening to fragmentation of the grains into smaller units. Jeffries and Archer,ll after carefully considering the problem of work-hardening from many angles, came to the conclusion that cold-working mechanically refines the grains into smaller crystal fragments, some of which at least differ in orientation from the parent grain. The increase in

Jan 1, 1940

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe&apos;s book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father ¬Dr. Samuel Gridley Howe, his mother-Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe&apos;s writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature. is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass . . . by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works "f the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By W. H. Nielson, L. S. Diaz

Several techniques are presented to adjust small errors inherent in data collected from material balance measurements on the flotation process. The basic technique used is a Lagrange multiplier adjustment of the filtered data taken from the equipment measurements. The raw data are adjusted such that material balances are closed. The adjustments to each data point is inversely proportional to the square of the standard error of measurement. Problem areas in equipment utilization are discussed. Typical results from on-line measurements are presented. This technique can be applied to either on-line process measurements or metallurgical test data.

Jan 1, 1973

By James Yancik

The Howe Coal Co. is mining the Oklahoma Lower Hartshorne bed which ranges in seam thickness from 38 to 42 in. and pitches approximately 7° to the northeast. The raw feed to the cleaning plant averages about 20% ash and 1.10% sulfur, being reduced in the cleaning process to 4.8% ash and 0.9% sulfur with a free swelling index of 8 or 8%. This coal rivals the Pocohantas seam in chemistry and coking characteristics but has better fluidity than the Pocohantas seam coal. The coal is presently being prepared for the Japanese steel market in an 85-tph pilot plant designed and constructed by Roberts & Schaefer. The cleaning-plant flowsheet is discussed in detail.

Jan 1, 1972