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By William D. Klopp

A study was conducted of the tensile and creep properties of are-melted and electron-beam-melted tungsten over the temperature range 2250° to 4140°F. The tensile and creep strengths vary with pain size, the finer -grained materials being stronger. The activation energy for transient creep at 2250° to 3500°F is 95,000 cal per (g)(mole), while that for steady creep at 3300o to 4000°F is 141,000 cal per (g)(mole). At 2875o to 3300°F the apparent activation energy for steady creep decreased with decreasing temperature. It is suggested that cross slip is rate controlling during transient creep, while dislocation climb is rate controlling during steady creep above 3300° F. ALTHOUGH considerable data have been generated on the high-temperature tensile properties of powder-metallurgy tungsten,1 relative few data have been published on the properties of are-melted2 or electron-beam melted tungsten.3 Furthermore, the available data show a fairly large amount of scatter at high temperatures. The effects of structure and purity have not yet been defined, aside from observations that high-purity electron-beam (EB)-melted tungsten3 and single-crystal-plasma-flame tungsten4 are weaker than less pure powder-metallurgy tungsten. The creep behavior of powder-metallurgy tungsten has been studied, but no data are available on the creep behavior of tungsten consolidated by melting. Green5 found that powder-metallurgy tungsten exhibited linear creep at 4082° to 5072°F with an activation energy of 160,000 cal per (g) (mole). The similarity of this activation energy to that of 153,000 cal per (g)(mole) for volume self-diffusion6 suggests that recovery of strain hardening by dislocation climb is rate controlling in this temperature range. In studies at 4800°F, Sutherland and Klopp7 concluded that grain size significantly affected the creep behavior of commercial powder-metallurgy materials. This grain-size effect was suggested by sherby,8 although the opposite relation had been reported for aluminum.' The purpose of the present study was twofold: first, to provide baseline data on high-temperature tensile and creep properties of are-melted and EB-melted tungsten for concurrent tungsten alloy studies, and, second, to determine the phenomenolo-gical effects of structural and purity variables on the high - temperature mechanical properties of tungsten. EXPERIMENTAL The are-melted tungsten materials were prepared by melting sintered 1-1/4-in.-diam electrodes into 2-1/2-in.-diam by 5-in.-long ingots. The are-melting facility has been described previously.' Eight ingots were melted, machined, and hot-extruded at

Jan 1, 1965

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By A. L. Holley

The intention of this paper is not to discuss this important subject in all its bearings, but merely to point out why mechanical tests of steel, as ordinarily made, are not, alone, of any special value to engineers—certainly not to general mechanical engineers. The agents of the Barrow Hematite Steel Company, one of the largest and most successful Bessemer establishments in England, have recently distributed a report, made by Sir William Fairbairn,

Jan 1, 1913

By Harrison Schmitt

SINCE the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Graton1 and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the Uni-versity of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central. or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1933

By James Johnston

Synopsis.-A description of the working of the mills of this company and the metallurgical practice in vogue, by which a remarkably. complex silver ore, averaging 54 oz. of silver per ton (run-of-mine ore), is treated to give a 95.66 per cent. extraction. The main features of the, processes are: The cyanide amalgamation of the high-grade ore. The cyanide treatment of the low-grade ore, after extremely fine grinding and close classification, in a caustic soda solution. The use of a wet desulphurizing process to break up refractory silver minerals. The substitution of aluminum dust for zinc dust as a precipitant. The recovery and shipment of over 13,000,000 oz. of silver in bullion at. 997 to 999 fine since this metallurgy was inaugurated, about 2.5 years ago. On the completion and successful operation of the mill to treat their . high-grade ore,1 the Nipissing Mining Co., under the general management of R. B. Watson, started a series of investigations of the possible treatment of the low-grade ore by the cyanide process, so that they would be in a position to market only silver bullion. These tests were run in July, 1911, on a large scale, by G. H. Clevenger, on an average mixture of Nipissing ore. The results obtained by a partial amalgamation followed by cyanide treatment gave an extraction varying from 90 to 93 per cent. and were sufficiently encouraging to warrant Charles Butters, the company's Consulting Metallurgist, in recommending that the new low-grade ore mill under contemplation should be a cyanide mill, instead of a concentrator. The cost of such a mill, capable of treating 200 tons per day, to obtain a 90 per cent. extraction at a working cost of $3 per ton of ore treated, was estimated at $250,000.

Jan 1, 1914

By AIME AIME

SILVER reached a new high, with the ceiling the limit, at the annual Institute dinner at the Commodore on Washington's Birthday night. Carrying along as ballast other commodities, such as rolls, roses and ferns, souvenir boxes and table number placards, hundreds of silvery balloons, cut loose from their moorings at the tables, bounced idly against the plaster decorations high overhead. At the head table, Scott Turner, retiring President, pre- sided as toastmaster, with the new President, Frederick M. Becket, on his right, and the Chairman of the New York Section, Sydney H. Ball, on his left. Many other distinguished Institute members, medalists, and representatives of organizations and committees, ranged to the east and west. Each had the opportunity at least to rise and bow.

Jan 1, 1933

By Stanley J. LeFond

Jan 1, 1985

By E. Swartzman, G. C. Behnke

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button. A method of analysis to be satisfactory not only for a scientific laboratory but also for use in industrial control laboratories under varying conditions should employ equipment which is rugged, easily calibrated, and readily replaceable by standard materials. Gas is not universally available as is electricity, and it is generally easier to calibrate and control a simple electric furnace or heater than a gas burner, the voltage not usually fluctuating to the degree that gas pressure does. Quartz crucibles are fragile, and the size specified in the test is not normally used for any other purpose in the laboratory. Although more expensive, the 15-cc platinum crucible, available in all laboratories where volatile matter in coal is determined by the standard ASTM method, is sturdy and standard and easily replaced. Because of these considerations, a modification of the standard method has been developed which employs a standard laboratory 350-w cone heater and standard 15-cc platinum crucibles. The results of numerous tests conducted with such apparatus show conclusively that the free-swelling index values as judged by the buttons produced with this equipment are exactly the same as those obtained by the standard gas burner method. Thus it is suggested that this electric cone heater method employing standard 15-cc platinum crucibles be considered as an alternative to the ASTM method, Designation: D720-46. The free-swelling index of coal is determined by means of the ASTM method, D720-46. This method, which is an adaptation of the crucible swelling test for coal of the British Standards Institution, consists of heating 1 g of coal in a special covered quartz crucible in a regulated gas flame for a period of not less than 2.5 min in which time the temperature of the inner surface of the bottom of the crucible reaches a temperature of 82025°C. The residual coke button is then compared in size and shape with a series of standard profiles shown in Fig. 1 and designated by number from 1 to 9 in increasing order of size. As the method is empirical, it requires rigid standardization of the apparatus and repeated calibration of the gas burner. The dimensions of the low form quartz crucible recommended must be rigidly adhered to as small variations in diameter or wall thickness result in variations in the rate of heat transmission and thus in the resultant size and shape of the coke button. The gas burner must be calibrated almost every time a new set of determina-

Jan 1, 1952

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By J. L. Lamont, W. Crafts

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By W. Crafts, J. L. Lamont

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By Donald C. Barton

The theory of gravitation is based on Newton's law that any two bodies exert a mutual attraction which is proportional to the product of their masses and inversely proportional to the square of the distance between them; i. e., A = KMRm2 (1) where K is a constant, M and m are the respective masses of the two bodies, and R the distance between them. In the earth's gravitational system, the earth is one of the bodies; the other may be any body within or without the earth. In theoretical discussions and calculations,in regard to gravity, that other body usually is taken as a unit of mass: in the C:. C:. S. system, a body of one gram in mass. Gravity and Level Surfaces Gravity is defined in geophysics as the force of attraction exerted by the earth, towards itself, on a body of unit mass. The intensity of gravity is usually expressed in dynes of force or in centimeters of acceleration In geophysical work in America, most commonly it is expressed in dynes (per gram) with the "per gram" understood and not directly expressed. In geophysical work in Europe, most commonly it is expressed in centimeters per second per second (cm. /sec.2) and less commonly lrierely as centimeter-gram-second units (c. g. s). At sea level, the intensity of gravity amounts very nearly to 980 dynes. The vertical is the direction along which the attraction of gravity is exerted at any point. In most cases, it is very nearly, but not quite, perpendicular to the earth's surface. The path that would be taken by a body falling freely through space toward the earth is vertical at each point and may be spoken of also as ('the vertical," or as the line of the vertical, or as a line of force of gravity. At the earth's surface it comrrlonly is very nearly, but not quite, a straight line.

Jan 1, 1929

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By J. J. Gilman, T. A. Read

FOLLOWING the deformation 01 zinc monocrys-tals, sharply bent basal planes are observed near several types of inhomogeneities. Three of these in-homogeneities have characteristics which are quite regular so that they can be studied and analyzed. These are compressive kink bands, "deformation bands," and the inhomogeneities near end restraints. The present paper describes experiments in which "deformation bands" were artificially produced, and bend plane phenomena are discussed in terms of dislocation theory. Also, two new bend plane phenomena are described. The importance of bend plane phenomena in the deformation of crystals is not widely recognized. Many phenomena may be explained in a manner similar to the discussion in this paper. Jillson1 has pointed out that the "punching effect" in zinc is a bend plane phenomenon and is not caused by prismatic slip.' Bowles3 has suggested that they may be involved in diffusionless phase changes. Cahn4 has discussed the role of bend plane formation in the polygonization of zinc. Experimental Work Tensile Kink Bands: Because of the geometrical similarity between "deformation bands" and "kink bands" (compare Fig. 1 of this paper with Fig. 1 of the paper by Hess and Barrett"), the band shown in Fig. 1 of this paper will be called a "tensile kink band," and that shown by Hess and Barrett will be called a "compressive kink band." It is felt that the term "deformation band" should be reserved for banded structures in polycrystalline materials such as iron." Tensile kink bands seem to form spontaneously in aluminum crystals deformed by tensile loading.7-10 In zinc and cadmium crystals they do not form in good, carefully loaded specimens.'." However, tensile kink bands can be produced artificially in zinc crystals. The present authors did this by scratching one of the flat surfaces of triangular crystals transversely with a sharp needle. Natural tensile kink bands caused by inhomogeneities sometimes appeared in deformed crystals which were identical in appearance with the artificially produced ones. Zinc monocrystals were grown by the Bridgman method in graphite molds. Chemically pure zinc (99.999+ pct Zn) was used and the molds were sealed inside evacuated pyrex tubes during growth. The crystal cross sections were equilateral triangles with a typical base of 0.210 in. The artificial kink band shown in Fig. 1 is typical of tensile kink bands in zinc. The band lies between two bend planes which run from upper right to lower left and is inclined oppositely to the slip bands which are sharply bent at the two bend planes. The general form of the artificial tensile kink bands was independent of the scratch depth (1 to 5 mils deep) and also independent of which side was scratched. These variables did cause variations, however. Deep scratches produced more localized kink bands than light scratches. Also, if the angle between the slip plane traces and a transverse scratch varied appreciably among the three sides, then localization of the resulting kink bands also varied. Furthermore, if the slip direction lay nearly parallel to the scratched side, the band was more developed near the scratched side than at the opposite edge. Scratches produced tensile kink bands for crystal orientations from xo = 15" to x, = 75". Fig. 2 shows a scratched crystal after deformation. One triangular side lies in the plane of the photograph. The right hand tensile kink band was produced by a transverse scratch on the upper right side. The next two kink bands were the result of scratches on the front surface. The kink band at the left was caused by a scratch on the lower back side. All four bands have the same general form. A longitudinal scratch was also made on the crystal shown in Fig. 2 to determine the effect of a scratch on the critical shear stress. The critical shear stress of the scratched region was 33.9 g per sq mm compared to 24.4 g per sq mm for the un-scratched region above it. Fig. 3 shows Laue patterns of the crystal shown in Fig. 2. Fig. 3a shows the pattern of the undeformed crystal. The orientation was x, = 21°, A, = 31". After deformation, Fig. 3b was made of the homogeneously deformed portion of the crystal. The spots are compact but split into two halves. This region was elongated 45 pct and its orientation was x = 14", X = 20"; the sine law predicts x = 14", A = 20.5". Fig. 3c was taken near the center of the middle tensile kink band of Fig. 2. The pattern shows a range of orientations and polygonization in this region. The spread in orientation was due to the fact that the basal planes were curved (see Fig. 1) rather than flat as in the ideal case. Some may also have been the result of elastic distortions and "local curvatures." The orientation range was x = 23" to 32", A = 30" to 42". It is apparent from Fig. 3 that the material inside and outside the kink band rotated in opposite directions with respect to the tension axis during deformation. The orientation calculated from the ideal configuration of Fig. 9,

Jan 1, 1954

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By D. W. Mitchell

J. H. Schlobohm (Joy Manufacturing Co., New York) —This paper has been read with a good deal of interest; however, there are several salient features which Mr. Mitchell has overlooked. The initial emphasis on selection should be placed on type of material to be loaded and method of mining involved. There is no possible connection in the comparison of scraper or Joy Lohite loaders with loaders of any other type. Neither can an operating comparison be made between "Rocker type" loaders and those equipped with loading head and gathering arms. Each unit has its application, but the application depends on material and the mining system involved. Mr. Mitchell's compilation of data on various loaders, while it represents a great many facts, does not represent true operational data, i.e. Table I, column heading "Max. Rated Capacity for 7 hr;" these figures are meaningless inasmuch as little or no time at all is allowed for tramming or switching or moving the loader from place to place. Table I, column heading, "Best Reported Field Shift," would be a better source of operational data, assuming of course that conditions, applicable to each class of loaders, were average to avoid enthusiastic performance figures. Table I, column heading, "Repair Parts Cost per Ton," is still another item which will not stand up under comparison unless the loaders involved are put into type classes, i.e., there are simply no means possible to show the repair costs of scraper loading versus a caterpillar mounted loader in abrasive material. The source of information here is also important. Actual field tests have proved that these costs are of a constant nature. Manufacturers are striving to hold them to a minimum and many interesting studies have been made. A fairly recent example of this in a large United States gold producer has proved that Joy HL-3 loaders can be consistently average, less than $0.025 per ton mucked. This cost represents repair labor and parts over a two year

Jan 1, 1952

Meeting, Aug. 20, 1913, B te, Montana, at 12.45 p.m.-On, the written request of 27 members of oft Institute residing in Montana, the Montana Local Section was established, and the following Committee was appointed by the President of the Institute to complete the organization : E. P. Mathewson, Chair pan; Frank M. Smith, Vice-Chairman; D. C. Bard, Secre-tary, Montana State School of Mines, Butte, Mont., Oscar Rohn, James L. Bruce. The President reported the appointment of a Committee on Mining Law, the names of whose officers and members are given on page xxxv of this Bulletin, and these appointments were approved. It was voted: That the Committee on dining Law be requested to establish a Sub-Committee on Censorship, a majority of whom shall be lawyers; and, further, that no paper on mining law be recommended for publication to the Committee on Papers and Publications, unless it is previously approved by the Sub-Committee on Censorship of the Committee on Mining Law. The President reported progress in the matter of co-operation between the Institute and the United States Bureau of Mines, through Committees of the Institute. The President reviewed the history of plans for a union or affiliation with the Mining and Metallurgical Society of America, and the following minute was then adopted : " The Board of Directors of the American Institute of Mining Engineers has carefully considered for several months the question of union or affiliation with the Mining and Metallurgical Society of America ; and, while at an earlier time and under other circumstances, such. a union might have been accomplished, yet under present circumstances the Directors of the Institute deem such union inexpedient. "While thanking the Mining and Metallurgical Society of America for its consideration of the matter, we believe that further discussion of the subject will serve no useful end, and we conclude it best that the Society and the Institute continue their useful functions and friendly relations side by side, as heretofore."

Jan 10, 1913