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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 H. Warlimont

In recent investigations of the microstructure and crystallographic features of martensite by electgon microscopy,', '9 thin films (about 50 to l000A in thickness) have been used as specimens. It was found by W. Pitschl ,2 that the lattice relationships between the supefiaturated fcc matrix and the martensite formed in thin films were different from those observed after transformation in bulk material. Corresponding differences are to be expected in nucleation and in reaction kinetics in the formation of martensite in thin films, but have not yet been reported. In the course of the preparation of thin films of iron-base alloys for investigation by electron microscopy it was observed that films of alloys, whose martensite formation temperature (Ms) was below room temperature, formed martensite during the electrochemical thinning process conducted at or above room temperature. The chemical compositions and approximate bulkM,-temperatures of the three materials on which this observation was made are listed in Table I. The alloys were vacuum-melted from high-purity metals. It can be seen that the effect occurred in alloys that contain only sub-stitutional components as well as in alloys that contain carbon as an interstitial solute. The appearance of martensite formed in this manner is illustrated in Fig. 1, which represents a polished film of alloy No. 1 at XI0 magnification. The martensite plates can be recognized by their surface relief effects. In addition, heavily strained (owrinkledo) austenite can be seen near the edges of the film where it is thinnest and transformation stresses or strains can be accommodated by plastic deformation most easily. The nonuniform distribution of transformed regions is probably due to the varying thickness of the film. These observations were common to all materials listed in Table I. Because effects of supercooling or straining can

Jan 1, 1962

By G. F. Butterworth

The metallographic structures most frequently encountered in rifle barrels, and which are illustrated by the accompanying photomicrographs, fall naturally into two groups, distinguished by the method used to, produce in the stock a physical condition having the requisite properties. The fist group consists of "rolled" barrels; that is, barrels subjected to hot working by rolling in or near the critical range. In the second group, the stock, which is smaller in diameter than the first, is upset to form the butt end and is then heat treated by giving it a quench and a draw. These barrels will be referred to as " heat-treated " barrels. The structure of the rolled barrels resembles closely that of the same steel after annealing. There is the same network of excess ferrite outlining the grain boundaries, but the grains themselves are composed of sorbite rather than pearlite. The grain size is closely related to the rolling temperature. The critical-point curves of this grade of steel, which is approximately 0.50 to 0.60 per cent. of carbon and 1.00 to 1.30 per cent, of manganese, show a single very pronounced point between 1300" and 1350" F. (704" and 732" C.). Barrels rolled within this temperature range give an exceedingly fine grain, shown in Fig. 1. In fact, the grains may be so fine that, at a low magnification, they may be confused with the heat-treated structure shown in Fig. 6. A magnification of 500 diameters, however, will always resolve a rolled barrel into the characteristic structure shown in Fig. 2. As the temperature is increased, the grains are found to be larger. If, on the other hand, the rolling temperature is below the critical range, the structure previous to rolling will not be obliterated, the only effect of rolling being to elongate the coarse sorbite grains in the direction of rolling, Fig. 3. This distortion is greatest at the muzzle. Heat-treated barrels are quenched in oil from above the critical range, which should give a martensitic structure, Fig. 4, but the presence of some troostite in the martensite is frequently noted when the quench has not been sufficiently drastic, Fig. 5. The structure brought about by the subsequent draw is not so striking, though quite as typical. It is sorbitic or sorbito-pearlitic, and under a low magnification appears almost homogeneous, as in the case of fine grains of pepper and salt well mixed together, Fig. 6. This structure is substantially the same for all

Jan 1, 1920

By Research Staff ? Verde Copper Mines

FLOTATION is now commonly practiced in alkaline ore pulps, yet little is known regarding the action of the alkaline solutions on the ore particles beyond the fact that films of oxidized material form. We wish to chronicle our discovery of the presence of soluble reducing agents in alkaline ore pulps of the United Verde, and present some data on lime consumption. During the grinding and flotation of a pyritic ore containing small amounts of ferrous sulfate and other soluble salts, an excess of lime was added to precipitate the salts, and filtered samples of the solution were titrated with standard permanganate solution. Even in pulps of high causticity an appreciable permanganate titration was always obtained, in spite of the fact that the solutions were shown to contain little iron. Investigation of the cause brought about the discovery of several previously unsuspected compounds in flotation pulps made from pyritic ore. Not only the reducing agents present had to be identified, but also the amount of dissolved oxygen, and a survey was finally made of the free oxygen content and reducing agents of the mill pulp in the concentrating mill at Clarkdale. A great many compounds might form, caused by oxidation of pyrite or other metal sulfides or by reaction between a lime solution and pyrite. The most probable compounds considered were calcium sulfides; polysul-fides, thiosulfates, and polythionates. Later it was discovered in the literature that in alkaline pulp polythionates do not exist and if introduced. are decomposed into sulfites and thiosulfates.1 Any precipitated sulfur is changed by alkali into thiosulfate and polysulfide. Sulfites and sulfides react to form thiosulfate, so that in the end it is possible to have in an alkaline solution only thiosulfate and an excess either of sulfide or sulfite. Confirmatory tests were made and it was finally established that the alkaline mill pulps made from the United Verde ore contained

Jan 1, 1929

By Arthur L. Hawthorne

10.1-1. Relative Position of Maintenance as Compared to the Overall Mining Costs. The basic issue regarding the importance of maintenance in the modern mining industry must be faced squarely by the top manage- ment of each company before any real progress can be made in organizing a maintenance program for optimum effectiveness. Just a few decades ago the maintenance at coal mines consisted primarily of a blacksmith for sharpening picks and shoeing mules; as a result, probably less than 5%of the total mining cost went to maintenance and some 80% was operating expenses (operating labor). With each succeeding advance in equipment design towards larger, more complex, and more productive units, the pendu- lum swings the other way. As an example, haulage trucks have progressed through various stages in the past 20 years from 15-ton units to a 240-ton truck now in the "shakedown" or experimental stage. The following com- parison between 15-ton, 50-ton, and 100-ton haulage trucks clearly illus- trates this changing cost pattern in terms of percent of overall costs for running each size unit. [Maintenance 24% 44 % 51 % Operating labor 59 % 33 % 16% Operating supplies (fuel oil) 4 %. 4% 3% Labor burden and vac. pay 6 % 4% 3% Depreciation Total] From the preceding figures it is interesting to note that, as a rule, operat- ing costs go down as the equipment gets larger and the maintenance costs increase with the larger units. This same trend in cost variation applies to nearly all mechanical equipment used in surface mining from the large

Jan 1, 1968

By V. Kondic, W. M. Rumball

HUNT and Jackson' have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson' typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil's terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E' plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E'; e.g., some 90 pct of normal systems lie below E' = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c' possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo's8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson's ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c', these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

By A. Bauer, P. Calder, N. H. Carr, G. R. Harris

Smallwood mine is part of the Iron Ore Company of Canada's Carol Lake operation and is situated in Labrador, 240 miles north of Sept-Iles, Quebec. Last year, 15 million tons of crude ore were crushed to yield 6.3 million tons of concentrate and pellets. This year the figures will be 17 million of crude and 7 ¼ million tons of concentrate and pellets, which is the full plant capacity. Carol Lake ores consist primarily of specularite and magnetite mixed with quartz. Since both rotary and jet piercing drills are used, it is often desirable in planning to know in which regions of the orebody, or new orebodies, a particular drill will be most economic. This makes it necessary to establish a correlation between drillability and pierceability and some physical rock property. For the rotary drills a good correlation was found with penetration rate and grinding factor index. The jet piercers were found to have a reciprocal relationship in the sense that the best rotary ground was the worst jet ground and vice versa. It is also indicated how an economic comparison could be made using these penetration rate versus grinding factor index curves, the hole size distribution curves for single pass and chambered holes, and the mine distribution curve for grinding factor index.

Jan 9, 1965

Albin, B. R Billings, Mont. '28 Amster, Nathan L . , 25 Broad St, New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave, Chicago, Ill. '28 Baum, Frank G Hobart Bldg., San Francisco, Cal. '28 Bayless, Ron. William S Russ Bldg , San Francisco, Cal. ' 28 Bean, Louts H., V.P., Dwight P. Robinson & Co, Inc 125 E. 46th St, New York, N Y. '23 Beatty, Ross J 1105 First National Bank Bldg., Chicago, Ill. '28 Benwell, Oswald F 205 Colorado National Bank, Denver, Colo. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Bingham, Charles W 1542 Hanna Bldg, Cleveland, Ohio. '28 Blumenthal, Hugo 44 Pine St, New York, N. Y. '28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H Iola, Kans. '28 Bragg, E. B Carmel, Cal. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1923

By A. M. Kivari

OPERATIONS at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials Closed-circuit grinding, classification, hydroseparation, flotation, agitation, and thickening are familiar terms at this cement plant These methods make it possible to process refractory limestone into suitable materials for the manufacture of modern cements Construction of the plant, haying originally a design capacity of 7000 bbl of cement per clay, was started in June 1939, and the first clinker was ground on the following Christmas Day At present the capacity is about 12,000 bbl of finished cement per 24 hr , most of the production being low-heat cement † About 3130 tons of limestone, 620 tons of clay and 100 tons of gypsum are required daily for this output Occasionally iron oxide is added to the clay to obtain the desired composition This, together with the gypsum, is purchased from outside sources Up to the present time, the corporation has produced low-heat, normal, moderate¬ heat, moderate-sulphate-resisting, high-early-strength, oil-well, modified-oil-well, and plastic cements Most of the present production is for Shasta Dam, near Redding, Calif , the told demand being 5,800,000 bbl of cement Following are sonic of the cement requirements of the Shasta D [im] specifications [ ] The average specific surface in the bin s sampled shill be not less Ulan 1800 sq cm per gram and no individual sample less thin 1600 sq centimeters Compressive strength The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2 75 parts fine testing sand, by weight, shall be equal to or greater thin the following

Jan 1, 1941

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By O. C. Ralston

Flotation is now commonly practiced in alkaline ore pulps, yet little is known regarding the action of the alkaline solutions on the ore particles beyond the fact that films of oxidized material form. We wish to chronicle our discovery of the presence of soluble reducing agents in alkaline ore pulps of the United Verde, and present some data on lime consumption. During the grinding and flotation of a pyritic ore containing small amounts of ferrous sulfate and other soluble salts, an excess of lime was added to precipitate the salts, and filtered samples of the solution were titrated with standard permanganate solution. Even in pulps of high causticity an appreciable permanganate titration was always obtained, in spite of the fact that the solutions were shown to contain little iron. Investigation of the cause brought about the discovery of several previously unsuspected compounds in flotation pulps made from pyritic ore. Not only the reducing agents present had to be identified, but also the amount of dissolved oxygen, and a survey was finally made of the free oxygen content and reducing agents of the mill pulp in the concentrating mill at Clarkdale. A great many compounds might form, caused by oxidation of pyrite or other metal sulfides or by reaction between a lime solution and pyrite. The most probable compounds considered were calcium sulfides, polysul-fides, thiosulfates, and polythionates. Later it was discovered in the literature that in alkaline pulp polythionates do not exist and if introduced are decomposed into sulfites and thiosu1fates.l Any precipitated sulfur is changed by alkali into thiosulfate and polysulfide. Sulfites and sulfides react to form thiosulfate, so that in the end it is possible to have in an alkaline solution only thiosulfate and an excess either of sulfide or sulfite. Confirmatory tests were made and it was finally established that the alkaline mill pulps made from the United Verde ore contained

Jan 1, 1930

By Robert L. Frantz

Progress and improvement continue to be the bywords of a dynamic coal industry. The industry continues to gain strength and expand its horizons in the face of competition from atomic energy and the problems of restrictive legislation. The direct contribution of coal mining and transportation to the national economy is about $3 billion a year ac- cording to a study made by the National Coal Policy conference. Coal remains the backbone of the power industry producing almost two-thirds of all the electrical energy generated by fossil fuels and one-quarter of all the energy consumed in the nation. Power supplied by electric utilities increased 6.9% last year. The chairman of the Federal Power Commission predicted a 7.5% growth rate until 1980 for the nation's electric output. Some 80,500 MW of fossil fired power plant capacity are on order or under construction before 1974, compared to a present capacity, all sources, of about 290,000 MW. The comparable new additions of nuclear power plants is expected to total about 51,000 MW.

Jan 2, 1969

By Research Staff ? Verde Copper Mines

FLOTATION is now commonly practiced in alkaline ore pulps, yet little is known regarding the action of the alkaline solutions on the ore particles beyond the fact that films of oxidized material form. We wish to chronicle our discovery of the presence of soluble reducing agents in alkaline ore pulps of the United Verde, and present some data on lime consumption. During the grinding and flotation of a pyritic ore containing small amounts of ferrous sulfate and other soluble salts, an excess of lime was added to precipitate the salts, and filtered samples of the solution were titrated with standard permanganate solution. Even in pulps of high causticity an appreciable permanganate titration was always obtained, in spite of the fact that the solutions were shown to contain little iron. Investigation of the cause brought about the discovery of several previously unsuspected compounds in flotation pulps made from pyritic ore. Not only the reducing agents present had to be identified, but also the amount of dissolved oxygen, and a survey was finally made of the free oxygen content and reducing agents of the mill pulp in the concentrating mill at Clarkdale. A great many. compounds might form, caused by oxidation of pyrite or other metal sulfides or by reaction between a lime solution and pyrite. The most probable compounds considered were calcium sulfides, polysulfides, thiosulfates, and polythionates. Later it was discovered in the literature that in alkaline pulp polythionates do not exist and if introduced are decomposed into sulfites and thiosulfates.1 Any precipitated sulfur is changed by alkali into thiosulfate and polysulfide. Sulfites and sulfides react to form thiosulfate, so that in the end it is possible to have in an alkaline solution only thiosulfate and an excess either of sulfide or sulfite. Confirmatory tests were made and it was finally established that the alkaline mill pulps made from the United Verde ore contained

Jan 1, 1929

By Louis D. Huntoon

CANADIAN gold production is forging ahead annually and the prospects are that it will continue to do so for many years. Table 1 shows recent annual increases. Production for 1933 will probably reach $70,000,000, and further increases are likely in 1934 and 1935. (Data for November and December, 1932, are estimated throughout this article.) The depression sent many prospectors to the woods so during the last two years many new gold areas have been discovered and are attracting real capital for exploration and development. Several mills came into production in 1932 and mills now under construction will start production in 1933. The offices of mining lawyers are busy. Capital for this new work is obtained from well financed mining companies, syndicates, and individuals who were fortunate enough to invest in the dividend-paying gold mines of the north country in the early days. Prospectors and capital are cooperating. An interest is always retained by the prospector or vender and usually a small amount of real money is given the prospector.

Jan 1, 1933

By P. van Meurs, C. van der Poel

From observations of the linear displacement of oil by water from a porous medium as visualized in transparent models, new insight into the mechanism of vircous fingering, as occurring in the case of unfavorable oil-water viscosity ratios, has been obtained. A mathematical description of the observed phenomena leads to formulas. expressing both oil production and pressure drop across the formation as a func-tion of cumulative water injection with the oil-water viscosity ratio as a parameter. Theoretical results are compared with those obtained from scaled laboratory experiments in sand-filled rubes in which water was injected at the one end and production was obtained from the other end. In the second part of the paper the same principles are used to calculate a more realistic production scheme in which production of oil and water is obtained from wells regularly distributed over the field. Results show satisfactory agreement with production data of an actual oil field. Application of the theory is extremely simple as only a limited number of readily available parameters have to be known and results are presented in an analytical form. INTRODUCTION When oil is displaced from a porous medium by water having a viscosity lower than the oil. the oil-water interface is essentially unstable and has the tendency to break up into what are called "fingers" or "streamers". This Viscous fingering has been noted before by Engelberts and Klinkenberg' and has recently been demonstrated in transparent models by van Meurs-. It is highly questionable whether it is at all possible to perform relative permeability measurements In the laboratory reproducing the same distribution of water and oil in the cores as Present in practice. Therefore, we based our descriptive theory on an idealized model which was "tailored" to the fingering mechanism as observed in transparent models under scaled conditions. This approach was the more attractive, as a highly simplified model had already yielded an adequate description of the process. Though we are aware our theoretical approach can be extended in several ways, it is given here in its simplest form to explain the fundamental principles and to avoid complicated formulas. SIMPLEST CASE OF A LINEAR DRIVE Observations and Theoretical Model In Fig. 1 a series of photographs shows how water penetrates into a formation saturated with an oil which is considerably more viscous than the water. The technique for obtaining these photographs, using transparent models, has already been described?. The fingers can be clearly observed and are seen to be mainly parallel to the flow direction. Note that the contours of these fingers are not smooth but show protrusions of water enclosing oil pockets.

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1'2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1'2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By Dae S. Young

A new probabilistic approach is introduced for slope stability analysis including adverse impact of blasting vibrations. The material strength within a slope area is randomized in this bi-variate joint probability analysis. To be a completely general engineering method, the new probabilistic approach employs the random variable transformation technique: the Hermite model of the Gaussian transformation function, which transforms the experimental histogram of strength values to the standard Gaussian variables. Because bi- normal joint probability is analyzed on the true probability region projected on the Gaussian transformed variable plane, it is an exact solution of slope stability based on the available sample data. Details of the probabilistic approach are given through a case study on an iron ore mine. The case study demonstrated that the probabilistic approach is effective and simple enough to be a routine engineering practice for slope analysis.

Jan 1, 1984

By D. E. Menzie, D. L. Dauben

This paper discusses the physical parameters involved in the slow flow of high molecular weight polymer solutions in porous media. The interacting effects of polymer properties and porous media properties on flow performance are considered. Experiments were conducted with the polyethylene oxides, with molecular weights ranging from 200,000 to over 5,000,000. Frontal advance velocities ranged from I to 30 ft/day. The porous matrix consisted of a flow cell packed with glass beads. Polymer solutions were characterized by viscosity and normal stress measurements. Under certain conditions, unexpectedly high flow resistance was observed. This behavior was observed to be a function of flow rate, pore size, polymer molecular weight and concentration. The polymer solutions exhibit "dilatant" flow behavior in porour media in contrast with the pseudo-plastic behavior in simple flow systems. A theoretical ex-planation of such behavior is presented. INTRODUCTION The use of polymers in the injected water of a waterflood increases oil displacement efficiency by reducing the mobility (k,/pu) of the driving phase. A reduced driving phase mobility results in improvements in the areal sweep efficiency and in the vertical coverage in stratified reservoirs. This mobility reduction may be achieved by a permeability reduction, a viscosity increase or by a combination of the two. Early attempts at increasing the injected water viscosity were not successful because of the poor economics involved. The use of such materials as glycerin, sugar or glycols to increase water viscosity was not economically feasible. Attempts in using certain naturally occurring polymers were not too successful because of the high polymer losses to the rock. A high molecular weight, partially hydrolyzed polyacry-lamide was introduced 3 years ago as a waterflood additive.',' Initial work by Pye' indicated that the presence of these polymers in dilute concentrations decreases the water mobility 5 to 20 times more than would be expected from measurements of the solution viscosity. Such an effect would be of obvious economic value since only a small polymer concentration would be required to accomplish a large reduction in water mobility. This research was designed to study the basic flow mech anisms of polymer solutions in porous media. The interacting effects of polymer properties and porous media properties on flow performance are considered. This study indicates some of the conditions under which these interactions can lead to significant mobility effects. is valid only for Newtonian fluids. For polymer solutions and other non-Newtonian fluids the equation must be modified to consider that viscosity is a variable quantity. Modification of the Darcy equation to include non-Newtonian effects has been the subject of several recent investigations."" The modifications generally adopt a rheological model. such as an Ellis or Dower law model. to Dorous media by defining some characteristic channel radius. Most of these studies showed the porous media flow behavior to be predictable from viscometric data. Investigations involving the flow of high molecular weight polyacrylamide solutions through cores have generally encountered the high flow resistances reported previously by Pye. This high flow resistance has generally been attributed to an in-depth permeability reduction, as evidenced by a reduced permeability to water which has displaced polymer solution from the porous media. Marshall and Metzner" report high flow resistances, which they attribute to viscoelastic effects. In this paper, the effects of polymer molecular weight, pore size, flow rate and concentration are considered. The polymers used are the polyethylene oxides known as Poly-ox. This class of polymers was used because of its availability in a wide range of molecular weights and because of its known ability to propagate well through porous media. THEORY PHYSICAL PROPERTIES OF POLYMER SOLUTIONS The polymer molecule dissolves in water by means of hydrogen bonding, but retains some of its own structural identity while in solution. Nonionic polymers, such as polyethylene oxide, are generally considered to have a random coiling configration. This type of molecule has the ability to "sequester" or hold a large volume of solvent within its coils in a manner similar to that of a sponge. The random coil is easily deformed and under an applied stress

By R. E. Gilchrist, R. F. Nielsen

When a gas is displaced by mother in a porous medium, and there is a relative immobile liquid present. there is a transition zone in which the gas composition varies from essentially that of the original gas to that of the injected gas. The change in extent of this zone with time may be governed by a mixing process in the direction of flow and by the rate of establishment of gas-liquid equilibrium, if the gases are appreciably soluble in the liquid. The relative importance of these two factors in deterri~ining the growth of the transition zone is discussed, with appropriate equations and experimental data. INTRODUCTION The various solution methods of oil recovery involve a transfer of the components of a mixture, whether within a single phase or between a liquid and gas. The similarity of a natural porous medium to systems used in separation and chromatographic processes makes it seem reasonable that certain concepts used by chemical engineers in "mass transfer" might be applicable to petroleum reservoirs. One approach, the HETP (height equivalent to a theoretical plate), involves a distance or length of time over which equilibrium might be con. sidered as established. Another approach involves direct use of a rate of mixing or rate of establishment of equilibrium. The latter approach has been preferred in relation to production problems. DISCUSSION AND PROCEDURE When a gas or liquid in a porous medium is displaced by one of different composition but miscible with it there will be set up a transition zone in which the composition varies from cssentially that of the original fluid to essentially that of the injected fluid. If the fluid being displaced is a gas, and there is a relatively immobile liquid present, the transition zone may be