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By Rudolph G. Wuerker

Charles T. Holland (Head, Dept. of Mining Engineeri*, Virginia Polytechnical Inst., Blacksburg, Va.) Mr. Wuerker has presented a very interesting discussion of the use of triaxial test methods for investigating the strength properties of rocks. Such methods, no doubt, eventually will develop considerable information of interest to those concerned with the design of mine layouts, particularly in the field of pillar design. From his discussion of my recent article, "Cause and Occurrence of Coal Mine Bumps" (Holland Mining Engineering 1958, p. 933-1002), it is evident that in one place at least I did not make my meaning clear to him and perhaps others. To clear the matter up I think it best to quote from the article, somewhat more fully than did Mr. Wuerker, as follows: "4) In actual operations — because rocksare not perfectly elastic, homogeneous, nor isotropic and because local yield does occur — the maximum stress as demonstrated by Phillips (Ref. 22, pp. 64, 65) and indicated by much experience in mining, does not occur at the walls of the opening but at a short distance inside the pillar. Furthermore, the maximum stress does not reach as great a value as theoretical considerations and laboratory experimental methods indicate.* Actual distance inside the pillar, measured from the wall, at which the maximum stress exists, has not been determined. Observations in many mines, however, indicate that this distance could have a mini-value of one to six or eight times the bed thickness and that it is probably affected by width and height of the opening, depth of cover, and relative values of the elasticity and plasticity of materials comprising the roof, floor, and coal seam. The actual value of the stress produced probably lies between the theoretical maximum and the average stress concentration that would be produced if the weight of the strata above the unsupported opening were evenly distributed over the pillars for a distance equal to the opening width." The footnote reference in the above quotation referred to the following: "*For example, the Pocahontas No. 4 coal bed in southern West Virginia is mined under cover up to 1800 ft thick. Development openings are driven 18 to 20 ft wide, and the bed is about 6 ft thick. According to the work of Panek, the tangential wall stress at mid-bed height under these conditions would reach values between 4000 and 5000 psi. Actual tests of 3-in. cubes of this coal show its compressive strength would be much less than this, perhaps as low as 400 psi. Yet the pillars usually show no evidence of failure in these headings. In this same bed at a depth of 800 ft, the author has seen an opening 225 ft between supports lying between two old groves approximately 1100 ft apart. According to the theoretical considerations, the stress in the pillar walls would have been about 18,000 psi, yet the pillar showed little or no evidence of weight. In view of these observations, it is clear that the wall stress does not attain the maximum values indicated by theory." (Underlining added to original wording.) By referring to Fig. 2A of my paper it will be noted that theoretically the maximum pillar stress would occur at the pillar wall, i.e., at the passageway surface of the pillar. Obviously this cannot be correct in the cases of stress ranging from 4000 to 18000 psi since the coal at the surface of the pillar is under no constraint and cannot have a strength much greater than 400 or 500 psi. Hence, my conclusion that the maximum stress does not occur at the wall but back in the pillar some distance from the wall. Since these stresses are pushed back in the pillar from the wall, it is also obvious that the loads transferred to the pillar from the opening will be spread over a greater area and hence Pillar stresses will not rise to the values postulated by theory and photoelastic experiment. Further since to visual inspection the coal along the pillar wall did not appear to be failed the conclusion was reached that the stress shift was caused by local elastic or plastic yield and by difference in the elastic modulus of the rocks composing the mine floor, mine roof, and coal bed. Later on under the heading "Strength of Mine Pillars" (pages 1000-1002) the effects of constraint is briefly described. Also a formula taking into account constraint is developed relating pillar strength to the uniaxial strength of coal and the L/T ratio of the pillar. Since my paper was written, reports of experiments conducted in South Africa (Denkhaus, et. al., 1959), in Sweden (Hast 19581, and in Canada (McInnes, et.al., 1959) reveal that the conclusion expressed relative to the existence of a low stress area existing around the edges of pillars and solid faces as described above is generally correct. But it seems possible that where the wall stress developed is less than the unconfined strength of the rock composing the pillar and where the roof, floor, and pillar

Jan 1, 1961

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By L. M. Yokum

Tremendous strides have been made in front end loaders in the last 15 years. Fifteen years ago a 21/4-cu-yd front end loader was the largest standard machine you could purchase. Today there are two commercially available 15-yd front end loaders and many 10-yd loaders. The estimated total worldwide market for all front end loaders over 1 cu yd has increased to over 30,000 units yearly. The trend for front end loaders, in general, and for the mining market, in particular, is to larger and larger loaders. Today there are 18 and 24-cu-yd front end loaders in prototype form. It is not inconceivable that within another 15 years there will be front end loaders in the 50-cu-yd class with design features quite different from today's. These larger loaders are being designed at the demand of the mining industry, and the design criteria are being directed at this market area. The costs of these larger loaders may be greater per unit of capacity, but it is the intent of the various manufacturers that they will be more reliable, be easier to service, give greater availability, live longer, and cost less to maintain, than previous loaders. It is also the intent of the manufacturers to compete directly with the large mining shovel as the front end loaders become appropriately larger and more reliable. There has been some trend in this direction in the past with smaller shovels and loaders. In Table 1 are data for U.S. production of front end loaders (5 to 6-cu-yd class and 10-cu-yd class) and U.S. production of cable-operated, crawler-mounted power shovels, draglines, and cranes (11/z to 5-cu-yd class) for the years 1965 and 1970 (Source: Bureau of Census, U.S. Department of Commerce). Many believe that the decline in shovel production, in particular, is due at least in part to the acceptance of the front end loader as a primary production tool. However, the foregoing comparison is for a smaller shovel class than for front end loaders. It has generally been a rule of thumb that a front end loader is competitive on a cost and production basis with a shovel when it is approximately twice as large as the shovel. This same relationship may not hold true with the larger 10 to 15-cu-yd electric shovels, but at some point, direct competition will probably occur. Current Trends There are many trends today that are significant. One major usage trend in large front end loaders involves load and carry operations. This application is defined as "performing the functions of loading, hauling and dumping with one machine over distances within its economical limits." Many people are using front end loaders to transport material as well as load it. It is estimated that nearly half of all 10-cu-yd front end loaders sold in 1970 went into primary load and carry work. Many times, significant savings result from using the load and carry system, instead of small truck and shovel operations, for distances in excess of 1000 ft. Strip mining in coal utilizes great numbers of front end loaders in this manner. In-pit crushing of limestone is developing on an ever-increasing level, especially in Europe, and this stimulates interest in load and carry operations. In Table 2 is a cost example for 10-cu-yd front end loader in a limestone quarry. More than likely, load and carry use will continue to increase over the next few years. While some types of mining do not lend themselves to load and carry in the pit, such areas as surge piles are applicable and should be studied. In the area of machine operating cost reduction, there

Jan 1, 1974

By A. H. Miller

THIS survey is one of the more recent tests of geophysical methods of prospecting by the Dominion Observatory and the Geological Survey of Canada, of which the purpose is to find out what application such methods may have to geological problems in Canada. The Malagash salt deposit lies on the north shore of Nova Scotia about 40 miles east of the New Brunswick boundary, and forms a part of faulted and folded Carboniferous strata. The salt beds are exposed only in the mine workings, which are about 1000 ft. deep and at one place extend for 1000 ft. along the strike. Lack of rock exposures, complicated folds, and faults make it impossible to predict the location of salt away from the mine. A survey of an area in the vicinity of the mine was therefore undertaken to find out whether the salt could be located by the torsion balance and whether its extension from the mine workings could be traced. As the gravitational effects at Malagash may be fairly typical of those at other concealed salt deposits in the Carboniferous rocks of the Maritime Provinces of Canada, the survey has a direct bearing on prospecting for other deposits. The survey was made in 1934 by A. H. Miller in collaboration with Dr. W. A. Bell, of the Geological Survey of Canada. Observations began on June 15 and were completed four months later, on Oct. 15. Definite gravitational effects including a lowering of gravity were observed over the deposit. The survey also disclosed one other area of low gravity east of the mine but whether this area is underlain by a large body of salt is not yet established.

Jan 1, 1936

By Fred H. Klaer

Water supplies dependent upon induced infiltration can be developed by vertical wells, by infiltration galleries, or by horizontal water collectors. Each method is described and the advantages of water obtained by induced infiltration with respect to cost, chemical quality, and temperature are shown by specific water supplies. THE subject of ground water in industry is assuming increasing importance as new processes and new industries are developed. Industrial specifications of chemical quality and temperature for process water and for cooling purposes are becoming more rigid, and water must now have many properties to meet these requirements. As ground water is usually more constant in quality and temperature, many industries are turning to ground-water supplies to satisfy their growing need. As many published articles have stated during the past several years, the ever increasing demands have caused shortages of water supply in many localities throughout the United States. Although such shortages are generally of a local nature, they have given rise to many attendant problems, such as increased pumping costs, salt water encroachment, and rising ground-water temperatures. One partial solution to the problems of overdevelopment of the ground-water reservoirs in many areas can be accomplished by developing ground-water supplies that are dependent upon induced infiltration and by planning the use of underground reservoirs. These reservoirs can be filled during periods of excess precipitation and stream flow and can be emptied during periods of drought, in a manner similar to the use of surface reservoirs. In this way water that otherwise would be wasted into the oceans is salvaged during periods of excess. The development of water supplies dependent on induced infiltration is a relatively new concept and should be defined. When a well is pumped, the water level around the well is lowered in the shape of an inverted cone or cone of depression. As pumping is continued, the cone of depression will continue to expand, horizontally and vertically, until the quantity of water crossing the perimeter of the cone plus the recharge within the area of the cone is equal to the quantity of water being pumped.

Jan 1, 1954

By C. V. Millikan, C. V. Sidwell

There is nothing more important in petroleum engineering than a definite knowledge of the pressure at the bottom of an oil well at any existing operating condition, and the relation of this pressure to the pressure within the producing formation. A knowledge of bottom-hole pressures is fundamental in determining the most efficient methods of recovery and the most efficient lifting procedure, yet there is less information about these pressures than about any other part of the general problem of producing oil. Determination of Bottom-hole Pressures Bottom-hole pressure may be calculated or determined by several methods. On an inactive well it may be calculated from the fluid head or, if the well is shut in, by adding the casinghead pressure, the static head of the gas and the fluid head. In wells flowing naturally through tubing the pressure at the bottom of the tubing may be calculated by adding the pressure at the casinghead between the tubing and the casing and the pressure due to the weight of the column of gas, but there is always possibility of error caused by fluid being in the annular space above the bottom of the tubing. If a well with tubing is flowing through either the annular space or the tubing, sufficient gas may be injected through the static space to insure that it is free of fluid but not sufficient to establish an appreciable friction loss. The pressure at the bottom of the tubing can then be calculated by adding to the pressure at the tubing head the pressure due to the weight of the column of gas. This is probably the most accurate method of calculating bottom-hole pressures. In wells flowing by gas-lift, the pressure at the point the gas enters the flow may be calculated by a gas-flow formula. Several types of pressure bombs have been used to measure the pressure at the bottom of wells. One is a piece of steel tubing with a check valve in the bottom and a connection for a pressure gage at the top. It is lowered into the well to the point at which the pressure is

Jan 1, 1931

By G. Y. Chin, A. R. Von Neida

The relationship between crystalline texture and magnetic anisotropy in a Co-10 pct Fe alloy has been investigated by means of X-ray pole .figures, hysteresis-loop tracings, and magnetic-torque measurements. The cold-rolled texture of a sample after 95 pct thickness reduction is of the "brass-type", that is, (110)[112/. At 500°C the cold-rolled material recrystallizes fo a (311)[112] orientation, plus a minor (210) [001] component. This texture persists up to 1400°C, at which point it is replaced by a secondary recrystallization texture, (111)[112]. Magnetic-torque measurements show that the easy axis of magnetization lies along the transverse direction in the cold-rolled material and changes to the rolling direction after primary recrystallization. This change is also reflected in the hysteresis characteristic; whereas the B-H loop along the rolling direction is nonsqunre with a low value of residual induction (750 vs 19,000 gauss at saturation) for the cold-rolled material, the annealed sample exhibits a very square loop with a large value of residual induction (16,000 gauss). Theoretical torque curves calculated from the texture data on the basis of magnetocystalline anisotropy energy compare favorably with the observed torque curves. Values of the crystal anisotropy constant, K1, obbained from these comparisons are in good quantitative agreement with single-crystal data. Furthermore, both the torque amplitude of the poly crystalline material and the magnitude of K1 obtained with a single crystal show an identical temperature dependence over the range from —195° 10 +220°C. It is thus conclzided that the magnetocrystalline anisotrpopy erlergy is chiefly I-esponsible. for the nzagnetic allisotropy of textured Co-10 pct Fe alloy. THE results of a study on the relationship between crystalline texture and magnetic anisotropy of an alloy containing 90 pct Co and 10 pct Fe by weight are reported in this paper. The alloy has an fcc structure: a saturation magnetization of about 19,000 gauss,2 and a nearly zero value of magnetoatriction.3 puzey4 has reported a large crystalline anisotropy constant of -7.4 X 105 ergs per cu cm, indicating the (111) directions as the easy axes of magnetization. Hence, texture variations resulting from cold work and annealing are expected to introduce a magnetic anisotropy in the polycrystalline material through the alignment of these (111) easy directions. In the present study, magnetic anisotropy of both rolled and annealed strips was determined by magnetic-torque measurements and hysteresis-loop tracings The results were correlated quantitatively with calculations based on texture data obtained by the X-ray pole-figure technique. It is established that the magnetocrystalline anisotropy energy is indeed chiefly responsible for the magnetic anisotropy of textured Co-10 pct Fe alloy. EXPERIMENTAL Material Preparation. The alloy nominally contained 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn by weight, the chief impurities being nickel, carbon, and silicon (less than 0.5 pct total). The cast ingot was rolled to strips 10 mils thick and slit to 1 in. in width. After strand annealing at 900°C in a hydrogen atmosphere, these strips were further cold-rolled to various thicknesses down to 0.25 mil (97.5 pct reduction), with samples collected for study of the development of texture and magnetic anisotropy as a function of thickness reduction. subsequently, samples cold-rolled from 100 mils to 0.25 mil were obtained, thus extending the thickness reduction range to 99.75 pct. In addition, 0.5-mil samples cold-rolled from 10 mils were selected

Jan 1, 1965

By S. Fisher Morris

THE New River coal-field embraces that portion of the Appalachian coal formation which lies on the waters of the New River, principally in Fayette and Raleigh counties, West Virginia, covering a strip of territory about forty miles in length along the line of the Chesapeake and Ohio Railroad from Quinnimont to Kanawha Falls, where the New River empties into the Kanawha, the railroad following the banks of the river the whole distance. (See map.) Between Kanawha Falls and the Valley of the Ohio lies the great Kanawha region, and these two coal-fields possess a greater variety of coal than can be found in any other portion of the country, enabling them to furnish the best fuels for any of the various demands of manufacture or domestic use, the Kanawha region possessing many varieties of gas, hard splint, and cannel coal, and the New River region bituminous and semi-bituminous, steam and coking coal. The New River, in its westward course towards the Kanawha, has cut its way entirely through the Seral conglomerate or No. XII of the Pennsylvania Reports, the Umbral red shales of No. XI appearing at the foot of the mountains at the eastern end of the region at Quinnimont, one of the upper ledges of the Conglomerate forming the summits; while at the western end, at Kanawha Falls, the top of the Conglomerate is nearly down to the level of the river, a portion of the " Lower Productive Measures" forming the greater portion of the mountains. These mountains rise abruptly from the banks of the river to a height of from 800 to 1200 feet, leaving only here and there narrow strips of bottom land, a few acres in extent; and as the measures consist principally of hard sandstones, shales, and conglomerates lying in a nearly horizontal position, the mountain-sides are very precipitous, with many long and high cliffs, which, with the great height of the mountains, give the country a very rugged appearance. Along the sides of these mountains fronting on the New River and its many tributaries there are exposed the outcroppings of several veins of bituminous and, semi-bituminous coal, varying in thickness from a few inches to over four feet, five of them being workable, or

Jan 1, 1880

By Andrew B. Crichton

No more important question has come before the coal industry in the past decade than the prevention of stream pollution by mine drainage; especially in Pennsylvania, where large areas of coal land have been developed. It may be thought that the problem of labor or lack of transportation outweighs in importance that of stream pollution. We can see possible remedies for labor and transportation problems but there is no known satisfactory solution of the mine-drainage problem. The subject has been given little serious attention, for, until recently, it has been little understood; but in the past year it was brought to the attention of the coal-mining industry by the introduction, in Congress, of several bills designed to prevent the discharge of acid waters from mines or other sources into navigable streams, or their tributaries. The first legislation proposed was the Applebybill, H.R.7369, designed particularly to prevent the oil pollution of coastal waters. It contained the following provisions, which the coal men regarded as referring to the coal industry. It shall be unlawful to throw ... any refuse matter of any kind ... into any navigable waters of the United States or into any tributaries of any navigable waters from which the same shall float or be washed into such navigable waters. The chemical, steel, paper, and other manufacturing industries, as well as the mining industry, objected to this clause, the miners claiming that it would prevent the discharge of waste or mine drainage into any waters of the United States, for all streams or tributaries finally reach navigable waters. The next bill introduced was that of Congressman Briggs, H.R. 7430, an amendment to Section 13 of the Pollution Act of March 3, 1899. The original act referred chiefly to oil and oil refuse, but it provided also "that no material of any kind should be deposited on the bank of a navigable water, or tributary, which might reach the waters and interfere with or

Jan 1, 1923

By J. T. Jones, H. V. Winchell

In the history of mining in this country there has been nothing exactly similar to the Mesabi iron-range in Minnesota, and the conditions there prevalent. Soft-ore mines are found in many parts of the country. In some the deposits are vertical, and are worked in open pits, or have been so worked, until it was found cheaper to go under ground. In other localities, the ore is scattered through clay beds in the form of hard lumps. These clay beds are sometimes excavated in open pits, and the ore separated by washing. On the Mesabi, the ore itself occurs in strata, and these strata appear quite flat to one standing upon the ground. The ore is soft in the main, and does not require much sorting to free it from foreign or deleterious substances. It is usually covered by the glacial drift-mantle, but occasionally passes beneath a capping of jasperoid rock called " taconite." The ore is twice or three times the thickness of the layer of drift lying upon it. This drift consists of clay, sand, and gravel, with occasional beds of large boulders. There is great difference of opinion among competent miners as to the cheapest methods of mining this ore. It is admitted that local conditions will govern largely ; but there is such a similarity among many of the mines that it seems possible to arrive at some general conclusions on the subject. A typical example of a Mesabi mine is found in the Biwabik. It is one of the largest, and is the most advanced in development. Not a single ton of ore has yet been shipped from this mine, but the expense of the explorations upon which the following description is based has exceeded $60,000. It is seldom that such accurate and complete exploration of a deposit of this magnitude has been possible in the space of time which has elapsed since the discovery of this ore-body. It lies in a new. region, and was remote from railroads until last August, yet, not only the width and length but the depth and quality of the ore-deposit have been learned, and the probable expense of' mining its 20,000,000 tons of ore has been closely figured. After careful consideration, the method of stripping and

Jan 1, 1893

By Andrew B. Crichton

No more important question has come before the coal industry in the past decade than the prevention of stream pollution by mine drainage; especially in Pennsylvania, where large areas of coal land have been developed. It may be thought that the problem of labor or lack of transportation outweighs in importance that of stream pollution. We can see possible remedies for labor and transportation problems but there is no known satisfactory solution of the mine-drainage problem. The subject has been given little serious attention, for, until recently, it has been little understood; but in the past year it was brought to the attention of the coal-mining industry by the introduction, in Congress, of several bills designed to prevent the discharge of acid waters from mines or other sources into navigable streams, or their tributaries. The first legislation proposed was the Applebybill, H.R.7369, designed particularly to prevent the oil pollution of coastal waters. It contained the following provisions, which the coal men regarded as referring to the coal industry. It shall be unlawful to throw ... any refuse matter of any kind ... into any navigable waters of the United States or into any tributaries of any navigable waters from which the same shall float or be washed into such navigable waters. The chemical, steel, paper, and other manufacturing industries, as well as the mining industry, objected to this clause, the miners claiming that it would prevent the discharge of waste or mine drainage into any waters of the United States, for all streams or tributaries finally reach navigable waters. The next bill introduced was that of Congressman Briggs, H.R. 7430, an amendment to Section 13 of the Pollution Act of March 3, 1899. The original act referred chiefly to oil and oil refuse, but it provided also "that no material of any kind should be deposited on the bank of a navigable water, or tributary, which might reach the waters and interfere with or

Jan 1, 1923

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 J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3') a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;' hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.' This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-' Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.' To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-' Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-' Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- ' and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10'1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.' only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

[University of Alaska College, Alaska Mining Society MAURICE BUTLER, President EARL FOSSE, Secretary RAYMOND J. BARBER, Faculty Sponsor R. H. OGBURN, Counselor University of California Berkeley, California Mining Association THEODORE OLSEN, President ARTHUR K BOURRET, Secretary FRANK H. PROBERT, Faculty Sponsor GRANVILLE S. BORDEN, Counselor D. C. JACKLING, Associate Counselor Carnegie Institute of Technology Pittsburgh, Pennsylvania The Metals Society EDWARD J. BOYLE, President W. T. LANKFORD, JR., Secretary M. GENSAMER, Faculty Sponsor EDGAR C. BAIN, Counselor]

Jan 1, 1940

By W. C. Lacy

A WIDE variety of metalliferous deposits in Peru shows a close and consistent relationship to intrusive and extrusive igneous rocks. This relation- ship furnishes a clue to the composition of ore-bearing fluids and to the timing in separation of these fluids from differentiation magma. Conclusions presented here are based on ten years' study of a large number of metalliferous deposits in Peru. The most important of these areas are shown in Fig. 1.

Jan 5, 1957

Jan 1, 1970

By J. P. Zannaras

Referring to the article by R. J. Charles and P. L. de Bruyn, let us assume that W = weight of glass bar; P = weight of hammer; e = total deformation; E = unit of deformation; K = potential stress energy; E = modulus of elasticity; L = length of the bar; 7, = coefficient of inertia; h = height, ft; V = velocity, fps; and a = cross section area. The portion of kinetic energy which is effective in producing stress energy in a fixed bar struck horizontally is given by the formula [ ]

Nov 1, 1956