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Jan 1, 1935

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Jan 1, 1946

By R. V. Norris

THE wage rates and working conditions in the anthracite. region of Pennsylvania have been governed for nearly 20 years by the award of the Anthracite Coal Strike Commission, appointed Oct. 16, 1902, by President Roosevelt. The report of this com-mission, made in March, 1903, was accepted and, with eight modifications made at various dates, has had .almost the force of law, and has kept this great indus-trial region free from strikes for almost a generation. In 1920, President Wilson appointed an Anthracite Coal Commission, and its report, accepted Aug. 30, 1920, governed wage conditions to April 1, 1922. Actually, the agreements have been for terms of two to four years, and lately, in 1916 and 1920, the employ-ees have continued at work pending the negotiation of new agreements which were made retroactive, and which have all been modifications of the original 1903 award. With the expiration, April 1, 1922, of the 1920 award approaching, Mr. Lewis, president, of the United Mine Workers of America, addressed a letter, on Feb. 20, to the operators, suggesting a meeting on March 15; this date was accepted by the latter, with the notation that the time was short. At the meeting, the Mine Workers presented 19 demands, and advised that if a satisfactory agreement was not reached by April 1.a suspension of mining would occur, contrary to the practice since 1916 of continuing work with a retro-active adjustment.

Jan 6, 1922

By H. E. Swanson

A description of the field apparatus has been published by D. G. Brubaker. Data from laboratory model studies of the in-line and broadside methods of operation are detailed. The conductor models include a single sheet conductor at several strike and dip angles and a schistose-type conductor. In addition, data on the effects of the strike length and of the depth of the conductor are presented for the broadside method of operation. All of the data show that the inclintion reverses direction over the top edge of dipping single sheet conductors. Differences between anomalies over conductors dipping between 90" and 30" are subtle,but flat-lying sheets can be readily distinguished from steeply dipping sheets. Schistose conductors are easily distinguished from single sheet conductors, and a procedure is given for determing the direction of schistosity. The depth of penetration under ideal conditions is 0.7 of the coil separation. In 1950, The New Jersey Zinc Co. (of Pa.) developed a lightweight apparatus for electromagnetic prospecting. A description of this apparatus has been published by D. G. Brubaker.1 It consists of a small, battery-powered vertical source coil and a direction-finding receiving coil. Source and receiver are kept a fixed distance apart and move as a unit along the survey lines. At each receiver station the inclination of the magnetic field created by the source is measured. Two methods of operation are used, in each of which measurements are taken with a constant source-to-receiver distance and with the plane of the source oriented to pass through the receiver station. In one procedure, called the in-line method, source and receiver travel in tandem along the same line. In the other procedure, called the broadside method, source and receiver move along adjacent lines, with the source-to-receiver direction oriented parallel to the assumed strike direction. The data recorded in either case are the inclinations, measured in degrees from the horizontal, of the magnetic field created by the source. These data are plotted at the receiver stations on a map. Scale-model studies of both methods of operation have been conducted in the laboratory and are reported in this paper. APPARATUS Small source and receiving coils wound with many turns of fine copper wire were used to produce and measure an alternating magnetic field in the same manner as the field apparatus. The model source coil was mounted in a vertical position and oriented so that the receiving coil was in the plane of the source. The receiving coil was mounted in a frame so it could be rotated to obtain the inclination measurements. The source coil was excited by a 100-kc signal generator. A tuned amplifier and a voltmeter were used to detect the null position of the receiving coil. The coils used in the field apparatus are usually spaced about 400 ft. The coils used in the model work were spaced from 4 in. to 4 ft apart. Thus the scale of the model work ranges between 1/1200 to 1/100 natural size. The model conductors were aluminum-coated building paper supported on wooden frames. The conductivity-thickness product was measured using a four-electrode system and was found to be about 300 ohms-'. CONDUCTIVITY CONSIDERATIONS The electromagnetic response from a thin sheet conductor is a function of the product of the conductivity of the sheet times the thickness of the sheet times the frequency of the alternating electromagnetic field times some linear dimension of the system such as the coil separation which indicates scale. The secondary electromagnetic field produced by the conductor increases in amplitude from zero at zero conductivity to a maximum value for infinite conductivity, while the phase of the secondary field with respect to the primary field shifts from 90" at zero conductivity to 0" at infinite conductivity. Several authors2-' have shown that most of both the increase in amplitude and the change in phase of the secondary field takes place over a three-decade range of the conductivity-thickness-frequency product. Only small changes in the amplitude and

Jan 1, 1961

CALAMINE is one of the semiminerals that have great similarity to the metals. It is a very heavy mineral earth of a yellowish color. It is found in Germany near the lead mines and in Italy in a mountain between Milan and Como. It is also found, as I have heard, in other places, as at Fosini in the territory of Siena. I believe that it is almost certain that some exists there because there are many other kinds of minerals there- about, although none is mined there in these times. But this does not mean that it could not be mined or that there is not some there that is real. Someone says that he med to melt what he could find with copper [36v]

Jan 1, 1942

By M. I. Kabir, R. S. Schechter, L. W. Lake

This paper presents the development and application of a novel scaling technique that, when used with a streamline model, causes a "bundle" of one-dimensional (1-D) problems to reduce to a single 1-D calculation. The 1-D bundle is the streamline representation of a two-dimensional (2-D) problem. The 1-D calculation accounts for chemical-rock interactions and the streamline model for areal sweep. The scaling technique significantly reduces computation time, is readily modified to desktop calculations, and can be applied to both absorbing and reacting species. The work was sponsored by the US Bureau of Mines.

Jan 1, 1986

By Frank Firmstone

IT is often desirable to obtain one or more accurate horizontal sections of a blast furnace after blowing out. Wishing to do this, last April, in the case of No. 4 furnace at Glendon, which had worn in a very remarkable manner, the method described below was employed, with very good results. A scaffold was fixed in the furnace, and on it was placed a drawing- board, covered with paper, the top of which was made level at exactly the height at which the section was to he taken. (Fig. 8.) The centre of the furnace (which had previously been found, and marked on a plank across the top) was laid off on it by dropping a plumb-bob from above, and a strong needle was driven into the board in the centre. By means of a straight-edge and two plumb- bobs, the line passing through the centres of the front and back arches was also drawn on the board. A pencil was fastened to a light wooden straight-edge at a known

Jan 1, 1875

By Frank Firmstone

It is often desirable to obtain one or more accurate horizontal sections of a blast furnace after blowing out. Wishing to do this, last April, in the case of No. 4 furnace at Glendon, which had worn in a very remarkable manner, the method described below was employed, with very good results. A scaffold was fixed in the furnace, and on it was placed a drawingboard, covered with paper, the top of which was made level at exactly the height at which the section was to he taken. (Fig. 8.) The centre of the furnace (which had previously been found, and marked on a plank across the top) was laid off on it by dropping a plumb-bob from above, and a strong needle was driven into the board in the centre. By means of a straight-edge and two plumbbobs, the line passing through the centres of the front and back arches was also drawn on the board. A pencil was fastened to a light wooden straight-edge at a known

By Herman Dykstra, R. L. Parsons

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By R. L. Parsons, Herman Dykstra

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

J. D. Fast and J. L. Meijering (Philips Research Laboratories, N. V. Philips' Gloeilampenfabrieken, Eindhoven, Netherlands)— After the departure of our friend Dijkstra to the United States, investigations on the effect of alloying elements on the behavior of nitrogen in a iron were continued in Eindhoven. We too found internal friction curves with two separate peaks for iron containing nitrogen in addition to 0.5 atomic pct V or 0.5 atomic pct Mo. Our first publication on these investigations" appeared almost simultaneously with the paper now under discussion. At first sight our experimental results seem to be in harmony with their conclusions, but a closer examination reveals that in the case of the Fe-V-N alloy the abnormal peak is not controlled by one time of relaxation only. Whereas iron containing 0.5 atomic pct Mn or Mo absorbs an amount of nitrogen of about the same magnitude as that absorbed by pure iron under identical conditions, iron containing vanadium absorbs in addition one nitrogen atom for every vanadium atom. This last amount, far exceeding the first amount in the case under consideration, combines chemically with the vanadium and causes no internal friction. The "free" nitrogen in the vanadium alloy gives rise not only to a damping peak corresponding to that in pure iron but— due to the presence of VN particles in the metal—also to the abnormal peak at higher temperatures. The VN particles create interstitial sites around themselves where the free nitrogen atoms are bound much tighter than in the normal interstices. These abnormal interstices, therefore, will capture free nitrogen atoms rapidly, whereupon these give rise to the abnormal damping. The binding energy in the abnormal interstices is not the same for all, and with coarsening of the VN precipitate the distribution of these energies is displaced toward the side of stronger binding. This is deduced from a shift of the summit of the second peak toward higher temperatures (from 80" to 88°C in our experiments) caused by prolonged heating at 950°C. From the intermediate state where they cause the abnormal damping, the nitrogen atoms pass over rather rapidly into the fully precipitated state (iron

Jan 1, 1954

By Raymond D. Daniels, Frank E. Rizzo, James D. Gerber

ThIS discussion describes a method for the addition of small amounts of oxygen to columbium (niobium) in an accurate and reproducible manner. The method is based on the complete reduction by columbium of a carefully weighed amount of another metal oxide. The equilibrium Pq associated with Cb-CbO mixtures is extremely low, e.g., 10"25 atm at 100O°C, and the pressures over Cb-0 solutions are even lower. The equilibrium Pq associated with a given metal-metal oxide mixture can be easily obtained, with the aid of a Richardson-Jeffes chart.' Although columbium should effectively reduce almost any metal-metal oxide combination, the proper choice of a metal-metal oxide system is complicated by the low rate of oxygen transport in the gas phase at low oxygen pressures and the difficulty in reducing any columbium suboxide formed during the reduction of the oxygen source material. Thermodynamically, oxide formation on columbium will be avoided so long as the oxygen partial pressure over the columbium is below the equilibrium pressure associated with the mixture Cb-CbO. The logical choice of a source for oxygen would appear to be a mixture of Cb-CbO, since oxide formation would be precluded by nucleation difficulty. But calculations using the kinetic theory of gasses indicate that, for a temperature of 900°C, the reaction would proceed too JAMES D. GERBER, formerly Research Assistant, University of Oklahoma, Norman, Okla., is Research Metallurgist, Air Force Weapons Test Laboratory, Kirtland Air Force Base, N. Mex. FRANK E. RIZZO, Junior Member AIME, formerly Assistant Professor of Metallurgy, University of Oklahoma, is Associate Professor of Metallurgy, University of Texas at El Paso, El Paso, Tex. RAYMOND D. DANIELS, Member AIME, Professor of Metallurgical Engineering, University of Oklahoma, is an NSF Fellow, Institute de MBtallurgie Structurale, Universite de euch:tel, Neuchitel, Switzerland. Manuscript submitted October 28, 1968. IMD

Jan 1, 1970

Albert Ladd Colby, New York, N. Y. (communication to the Secretary†):—I observed (Trans., xxxvii., 585) that to obtain tenders from several American mills, the foreign engineer should modify his maximum phosphorus to 0.10 per cent., not as Mr. E. Windsor Richards quotes me, that no American rail-maker can produce rails under 0.10 per cent. of phosphorus. Mr. Richards claims that no English engineer would agree to accept 0.10 per cent. of phosphorus on any terms whatever. Mr. Webster writes that only after an engineer has .been convinced that rails can be made in America equal in every respect to those he is getting abroad, should he be asked to modify ally conditions in his specifications. I know it to be a fact that during recent years in many cases, as, for instance, When delivery could be secured more promptly in the United States than in Europe, the consulting engineers of several British and colonial railroads have frequently agreed to modify their phosphorus requirement to a maximum of 0.10 per cent., and the rails delivered' under these modified specifications have, under like conditions, given just as satisfactory service and proved to be no more brittle than similar sections of 0.07 per cent. phosphorus rails, rolled in England under the same specification except without modification as to phosphorus. Furthermore, it would appear from the analyses of British rails, quoted by E. A. Dancaster,2 in his discussion of Mr.

Jan 1, 1908

By Robert L. Russell, Henry W. Zimmerman

The Bunker Hill mine in the Coeur d'Alene mining district at Kellogg, Idaho, has been a major producer of Pb-Ag-Zn ores since its discovery in 1887. The mine has produced over 29 million tons of ore from some 20 to 25 veins and ore zones and now covers an area approximately 1 mi long by 0.5 mi wide. The active section of the mine extends from 2500 ft above sea level to 1600 ft below sea level. Ore production is presently at the rate of about 1700 tpd. A 2-mi adit, the Kellogg tunnel, at the 2500 elevation provides access to the main shaft area. Ore is hoisted to the adit level through a 5000-ft. 50º-inclined shaft extending to the lowermost haulage level 1200 ft below sea level. Primary shaft service for men and materials is supplied by three major internal inclined shafts equipped with double-drum hoists. Present production requires ten levels to serve for main line track haulage. These range up to 5000 ft in length and are either 200 or 400 vertical ft apart. Also, many intermediate levels exist throughout the mine.

Jan 1, 1971

By R. G. Ward, A. E. El-Mehairy

A technique was developed to calculate the density of liquid metals from the profile of a weighed levitated drop obtained by emitted light photography and calibration. The density of liquid copper was determined over the temperature range 1370" to 2100°K and expressed with the equation: The molar volumes and thermal coefficients of expansion are calculated. Copper, upon melting, was found to expand 3.34 pct. A knowledge of the density of liquid metals is essential as it is a parameter appearing in most theories of the liquid state. The liquid density is also necessary for the calculation of the commercially important contraction occurring on solidification. Unfortunately good density values are rarely available and the present work was undertaken to establish a new method of density determination free from the limitations of the existing methods. For liquid metals with high melting points, the variation and the limited number of density values reported in the literature have been caused primarily by difficulties in technique, a matter which has been adequately discussed by Urbain.' In all the methods used for measuring the density of the high-melting liquid metals there are sources of error, and corrections have to be made. For example, in the method of balanced columns, the formation of gas bubbles in one or both arms was a great source of error. In the pyknometer3 and immersed-sinker methods, corrections of certain volumes for thermal expansion to the operating temperature exceed 4 pct. In the maximum-bubble method5 a correction for the thermal expansion of the bubble-tube is used (about 1.6 pct); a second correction takes into account the change in the volume of liquid displaced by the bubble-tube (about 3.5 pct). Another method used is based on the shape of a drop of liquid, at rest on an inert refractory plaque, obtained photographically or radiographi-cally. The volume is calculated from the shape, which is sensitive to the surface tension and supporting material, by some intricate empirical relation. The drop contour changes with 90 deg rotation of the support.7 The application of all methods is limited by reaction between liquid metal and the apparatus. The successful stabilization of a mass of liquid metal during levitation melting8 afforded a technique for measuring the density of liquid metals out of contact with solid materials. The technique was developed by using copper as the density of liquid copper has already been studied extensively, thus allowing comparison with the new method. It consists of calculating the volume from the dimensioned profile of the levitated drop obtained by emitted-light photography and careful calibration. The molten egg-shaped drop spins around the magnetic axis of the coil (lined vertically) at a speed which seems to increase with increasing temperature. The method does not involve corrections and the experimental setup allows the use of vacuum or special atmospheres. The maximum operating temperature is limited by excessive evaporation of metal from the droplet. EXPERIMENTAL Levitating System. A stabilizing ring was used in conjunction with a 3-turn levitating coil energized by a 450-kc per sec, 10-kw Toccotron with a high current-low voltage output stabilized to f 1 pet.' APyrex glass tube with a Pyrex Optical flat window inserted through the coil and ring allowed the use of special atmospheres during levitation melting, as shown in Fig. 1. Optical System. Fig. 1 shows the optical arrangement used to photograph the profiles of the drop, parallel and perpendicular to the vertical spinning axis, simultaneously on the same frame of a high-speed 35-mm film. The optical system was adjusted to avoid any distortion of the profiles and to ensure that both profiles are in focus. The length of path from object to objective was about 30 cm, and a magnification factor close to 1 was obtained with the single-lens reflex-camera system. Temperature Measurement and Control. In operation, the specimen temperature was constant to 5 C for a fixed power input to the levitating coil and fixed rate of gas flow through the tube. The temperature was measured by an automatic two-color pyrometer (Coloratio) checked at the melting

Jan 1, 1963

By Ernest Burchard

FLUORSPAR is found in most of the states from the Rocky Mountains westward, and commercial production of the mineral has been reported from Arizona, Colorado, Nevada, New Mexico, Utah and Washington. The map in Fig. 1 indicates the general distribution of many of these deposits but it is by no means complete. In the summer of 1926 the writer examined certain deposits of fluor-spar in Arizona, California, Colorado, New Mexico and Washington; in November, 1927, revisited the Jamestown, Colo., district, and in earlier years examined deposits in Colorado and New Mexico. Based on notes of his own and. on descriptions and other data by H. A. Aurand, H. W. Davis, R. B. Ladoo, V. C. Heikes, W. D. Johnston, Jr., and by producers of fluorspar, he prepared the following brief descriptions of deposits and estimates of reserves of fluorspar, originally for the use of the subcommittee on fluorspar of the Joint Committee on Foreign and Domestic Mining Policy and on Industrial Preparedness respectively of the Mining and Metallurgical Society of America and the American Institute of Mining and Metallurgical Engineers. Descriptions of many fluorspar deposits in various western states and districts have been published. It is not feasible to summarize this literature here, but the appended bibliography will indicate to the interested reader what papers are available.

Jan 1, 1933

By W. R. Shimer

(New York Meeting, October, 1913.) THE investigation herein described was carried out for the purpose of studying, both by chemical and metal-lographical means, the extent of over-oxidation of steel that can be accomplished by excessive over-blowing in a Bessemer converter. In addition there are appended some results of basic. open hearth and crucible steels. Remarks on Chemical Methods. The test block used was hemispherical in shape, 4.5 in, in diameter and 2 in. thick. Drillings for analysis were obtained by drilling through the entire solid part of the. block, carefully avoiding all cracks anti blow-holes and mixing these drillings thoroughly. Drillings were carefully examined for scale and the finest were gone over with a microscope to be sure all scale from whatever source had been. removed. Oxygen was determined by the well-known method of Ledebur, modified according to Cushman,1 with, however, the removal of the preheating tube, which was found unnecessary. This method has been found to give concordant results. Blanks run from 0.0003 to 0.0006 g. Duplicate determinations varied not more than 0.001 to 0.003 per cent. It seems to be generally supposed that the hydrogen method gives only that oxygen which is combined with iron. Whether this be true or not, the content of oxygen existing as iron oxide no doubt predominates sufficiently, so that the result obtained is sufficient to indicate whether the steel is over-oxidized or not.

Jan 9, 1913

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

Jan 1, 1902

By J. J. Gilvarry, B. H. Bergstorm

The first part of this paper describes a new approach to the problem of energy relationships in fracture and comminution. The basic theoretical method used (as contrasted to previous empirical or semi-empirical approaches) is an attempt to verify or disprove the hypothesis of von Rittinger, In the second part of the paper, theoretical conclusions for the three headings of single fracture, plural fracture, and comminution are tested. Agreement between theory and experimental results is demonstrated. The classical hypotheses on the energy relationship in brittle fracture are those of von Rittinger-that the energy required is proportional to the new surface formed— and the alternative one of Kick.' Over the years, repeated attempts have been made to discriminate experimentally between the two assumptions, or to replace both of them, as has been done by Bond? However, no semblance of agreement seems to exist among different investigators. This paper is the first in a series essaying a new approach to the entire problem of energy relationships in fracture and comminution. The purpose of this program of research is to verify (or disprove) the hypothesis of von Rittinger. In contrast to previous empirical or semi-empirical approaches to the problem, the basic method adopted is theoretical. The prime aim is to determine the distribution function for fragment size theoretically and to verify the predicted distribution experimentally. This approach should make possible determination of the total surface of the particles by integration over the corresponding distribution function; one may hope that this direct procedure will yield more definitive results than use of gas adsorption or other methods. The surface area so obtained can then be compared with experimental energies, as obtained by Bergstrom, Sollenberger, and Mitchell,4 for example. It is convenient to distinguish between single fratture, plural fracture, and comminution. Single fracture of a brittle solid is defined as fracture by an external stress system which is removed instantly and permanently when fracture is initiated. Plural fracture consists of single fracture of the original specimen, followed by a sequence of only a few secondary fractures; comminution differs in that the sequence of secondary fractures consists of a large number of repetitive steps. For single fracture, Gilvarrys has given a rigorous derivation of the proper distribution function for fragment size, based on a closely defined physical model and deduced strictly by the laws of probability. Gilvarry and Bergstrome have compared the predictions of the theory with experiment, and have found excellent agreement. The prior work of Gilvarry and of Gilvarry and Bergstrom considers only single and plural fracture. The purpose of the present paper is to extend the discussion to the case of comminution. For prefatory purposes, the theory of Gilvarry for single fracture will be outlined. The considerations will then be applied to the cases of plural fracture and comminution. SINGLE FRACTURE The derivation is based on the Poisson law.7 For Points distributed with mean density y over a domain, this law states that the probability p(t)dt of one point lying in the range t to t + dt with none in the interval 0 to Ms p(t)dt = ye-yt dt. For this distribution to be valid, it is necessary and sufficient that the points be distributed at random, individually and collectively in the sense of ~~~.7 The former qualification requires that the position of One Point be independent of another, and the latter implies that the probability of a region containing a

Jan 1, 1961