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By Francis B. Foley

Fundamentally, slag control in acid open-hearth steelmaking cannot be considered from any different viewpoint than can that in basic open-hearth melting. The same laws of mass action and distribution apply in both cases, so that while most, if not all, of the recent intensive study of slag-metal reactions have been carried on in basic furnaces the principles evolved are nevertheless applicable to acid open-hearth steelmaking and it is therefore not our intention to discuss the various possible chemical reactions in the slag and between slag and metal. The points we have to carry in mind, in considering acid melting practice, are the differences in the type of steels produced and the difference in the chemistry of both the steel and the slag. The acid furnace is used to produce, let us not say "quality" steel, for, after all, a "quality" steel for one purpose is not a "quality" steel for another, but steels that require acid melting practice to be of proper "quality." Steels that are required to have high physical properties in tests taken transversely from forgings are peculiarly the product of acid furnaces. In this class may be placed various ordnance materials, notably gun forgings and projectiles and large commercial forgings requiring high transverse ductility. Forgings requiring an extremely hard surface, polished and free from imperfections, are also typical acid-steel products. Of course, such forgings can be made of basic open-hearth steel, but not with the same assurance of success. At the start, the preparation of the slag in the acid and basic furnaces differs. Lime is charged in the beginning of a basic heat to form a slag, but in the acid furnace nothing is added for the special purpose of producing a slag when the heat is melted down. The result is that the acid furnace has much less volume of slag than the basic. The slag formed upon melting down is made up almost entirely of the oxides of elements contained in the metallic charge, notably oxides of iron, manganese and silicon, the amount of silica being augmented somewhat by erosion of the furnace lining. A typical acid open-hearth slag, when the bath is completely melted, will have an analysis about as follows: CaO, 3.40 per cent; SiO2, 51.9; Fe2O3, 1.25 ; FeO, 28.86; Al2o3, 1.82; MnO, 12.22. The high iron oxide content of the slag gives it a black appearance. The metal is high in carbon and some manganese and silicon will be present, depending on the amount in the original charge, the amount of

Jan 1, 1935

VITRIOL is likewise a mineral substance from whose exhalation, according to the opinion of some, are generated and produced the elemental materials or substances which produce metals, particularly gold. It is not a fumosity from metal nor is it a thing from which metal is extracted in any manner, although it shows in certain ways that it is not entirely without metal since it produces a certain trace of it. It is a thing that has a great resemblance to alum; it has a biting substance, is sharp to the taste and pungent to the tongue, and has an astringent nature. It dissolves in water and every damp place in a short time. They say that the reason for this lies, as with every other mineral, in its poorly joined watery substances. Nor does this mean that it does not contain much earthiness; on the contrary it seems to me that there are in it five. [2.9v] different participating qualities, that is, the property of sulphur, the action of alum, the corrosion of niter or of salt, and from the metals, the properties of copper and of iron. Its ore is mined in the valleys of mountains in wild but not too rugged places. It is more a gray earth or soft dead rock than a hard stone. It always has in it some yellow and green spots or near it is some sulphur mineral, either large or small.. When it is beneath the earth it exhales a sharp and very strong foul odor of scorching similar to that of sulphur. And the waters that rise where it is are all foul, earthy, and thick, some boiling with great fumes and others without great fumes, so that they surely appear to be infernal products in many places where there is a large quantity of it. After you have excavated and sorted well the quantity you wish, the ore must be put in a heap in open airy places before the vitriol can be extracted from this soil or ore, however you wish to call it. And it is left thus exposed to the weathering of the rains, the cold, and the sun for five or six months. It must be turned several times in order to bring to the surface that which was underneath; and always when this is done it is broken small with the eye of a mattock so that it is better heated and baked throughout. When it has been brought to this point it is covered over by a shed built above it or it is carried under a hut that has already been made. Here it is left to stand for another six or eight months before it is worked.

Jan 1, 1942

By L. Grånäs, B. Aronsson

In a recent study of Fe-Si alloys Walter and Koch' observed pairs of dislocations in Fe-6.25 pct Si crystals rolled to reductions of 10 pct and subsequently annealed for 1 hr at 650°C. They interpreted these pairs as being due to stacking faults. From the spacing of the dislocations a stacking-fault energy of 15 to 19 ergs per sq cm was calculated. These authors did not pay any attention to the order -disorder phenomena in Fe-Si alloys. It is the purpose of this communication to report some preliminary results from a study of ordering and its influence on the plastic deformation of Fe-6.0 pct Si alloys. Our results suggest that the dislocation pairs observed by Walter and Koch may have been due to long-range order rather than to stacking faults. The alloys used in this investigation were prepared from pure electrolytic iron and silicon and were melted in argon. After hot working, strip tensile specimens were machined to a gage length of 70 mm and a thickness of 1 mm. The specimens were heat- treated for 2 hr at 1000°C, furnace-cooled, and subsequently deformed 2 pct in tension at 400°C. The strain rate was 5.6 X lo-' sec-'. Thin foils of the deformed specimens were prepared by means of the Bollman technique and examined in a Siemens Elmis-kop I at an accelerating voltage of 100 kv. In the Fe-Si system long-range ordering occurs at a silicon content of about 6 pct Si. In our alloys evidence for ordering is given by selected-area diffraction patterns which show extra reflections consistent with a super lattice of the D0 9 type. In addition, the dislocation arrangement in deformed specimens indicates that long-range order is present. A typical mi-crophotograph of a thin foil is shown in Fig. l. The dislocations are usually straight and parallel and laying in distinct directions. In the commonly observed (111) zone the projections of the dislocations are close to (113) and (oil). Observation of the image position indicates that the two dislocations in a pair have the same Burgers vector and hence constitute a superlattice dislocation.~ According to theory3 a superlattice dislocation in the DO3 structure consists of four ordinary dislocations connected by two types of antiphase boundaries as shown in Fig. 2. In our specimens only two dislocations in each pair have been observed, Fig. 1. The problem is to decide whether the area between these is a NN or a NNN antiphase boundary. Dark-field images using the (200) reflexion (the indices are defined with respect to the DO3-type superlattice) can

Jan 1, 1968

By W. A. Mudge

This discussion will be limited to malleable, commercially pure nickel and some high-nickel alloys, containing more than 50 per cent of nickel, which are produced by The International Nickel Company, Inc. at its Huntington works, West Virginia, from electrolytic nickel or from a nickel-copper sulphide matte. The principal sources of nickel are sulphides of nickel, copper and iron, which are found in the large deposit of pyrrhotite-pentlandite-chalcopyrite ores in the Sudbury area of Ontario, Canada. Pentlandite, a complex nickel-iron sulphide, is the nickel carrier. These ores are concentrated, roasted, and smelted to remove considerable iron and sulphur and to produce a nickel-copper sulphide matte. Separation of the component sulphides of this matte, followed by electrolytic refining, results in the production of electrolytic nickel and electrolytic copper; direct refining of a selected portion of the matte gives the nickel-copper alloy, Monel. FUNDAMENTAL OPERATIONS Melting of the metallic materials is done in natural gas-fired, acid furnaces of the open-hearth, or reverberatory, type, having capacities of 6 to 20 tons; in three-phase, basic, electric-arc furnaces, having capacities of 7 to 20 tons; and in basic, high-frequency induction furnaces having capacities of ½ to 3 tons. Malleable, commercially pure nickel is melted in the acid open-hearth furnace. The charge is sulphur-free, electrolytic nickel, containing 99.9 per cent nickel* and clean mill scrap. Monel, containing approximately two thirds nickel and one third copper, is produced by roasting the nickel-copper sulphide matte to an oxide, smelting the oxide with charcoal in a 20-ton, acid open-hearth furnace, adding clean mill scrap, duplexing to a 20-ton, basic, electric-arc furnace, and refining in this furnace with a lime-fluorspar, carbide slag. Inconel, containing nickel, 80 per cent; chromium, 14 and iron, 6, is melted in the 7-ton electric-arc furnace or the 3-ton induction furnace. The charge is electrolytic nickel, ferrochromium and clean mill scrap. These are the fundamental operations. High-nickel alloys are produced from one of these three materials by additions of suitable amounts of manganese, aluminum, silicon or copper. For example, the age-hardenable alloy, K Monel, is produced from Monel by the addition of approximately 3 per cent of aluminum, and D nickel is produced from nickel by the addition of approximately 4.5 per cent of metallic manganese. For conversion to rods, bars, sheet, strip, tubing and wire forms, by hot-working and cold-working operations, the molten materials are teemed into ingots ranging in size from 14 by 14 by 60 in., 3300 lb., to 36 by 36 by 48 in., 18,000 lb. All ingots are overhauled mechanically before hot working.

Jan 1, 1946

By Fred C. Bond

THE process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in, common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. FORMULA FOR BALL WEAR Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1940

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process. The laboratory investigations involve high speed photography where the dynamic fracture process is recorded with a Cranz-Schardin 1, 2 multiple-spark camera. The camera is equipped with 16 spark gaps which are pulsed at 25 K volts to produce an intense but very short (0.5 sec) flash of light. The camera is capable of recording 16 photographs of a dynamic event at framing rates which can be varied from 30,000 to 1,500,000 frames per second. The exposure time is sufficiently short to stop motion associated with detonating explosive charges and to make visible the details of the fracture process at a bore hose. The bore hole in a massive intact rock formation is modelled with a two dimensional plate containing a circular hole to represent the bore hole. The model material employed is a transparent polyester known commercially as Homalite 100.* This polymeric material is extremely brittle as evidenced by its extremely low fracture toughness of [ ]. The fracture toughness is a measure of the ability of a material to resist the propagation of flaws or small cracks. In comparison, Schmidt3 has recently measured the fracture toughness of Salem limestone and determined [ ]. Thus, the Homalite 100 should closely model the brittle nature of rock where fractures occur at small flaws and propagate without any apparent plastic deformation. Homalite 100 is also birefringent, which indicates that it becomes optically anisotropic when subjected to either static or dynamic loads. Circularly polarized light is transmitted through the loaded Homalite 100 model in a polariscope4 and the birefringence produces an optical interference pattern which is called a fringe pattern. For dynamic photoelasticity, the multiple-spark camera is equipped with polaroid filters to produce the circularly polarized light required to generate the photoelastic fringe patterns. An example of a singlespark frame showing a fringe pattern from a typical experiment is presented in [Fig. 1]. The photograph was taken 0.000072 sec (72 sec) after the detonation of the explosive charge. The circular fringes are due to the outgoing dilatational or P type stress wave and travel with a velocity of 85,000 in. per sec (2260 m/sec) in the Homalite 100. The P wave is followed by a second lower velocity stress wave known as the shear or S type wave which propagates at a velocity of 49,000 in. per sec (1245 m/sec). In the local neighborhood of the bore hole, several radial cracks are visible. These cracks propagate at essentially a constant velocity of 15,000 in. per sec (380 m/sec) prior to arrest. The fringes about the crack tips and in the local region of the bore hole are primarily due to the residual gases contained in the bore hole after the explosive charge was detonated. Sixteen frames similar to this one are recorded during the experiment to give full field visualization of the dynamic event at 16 discrete times over its duration. The fringe order number N is related to the difference in the principal stresses of and 02 according to a stress optic law4: [ ] where f0 = material fringe value, and h = model thickness. The wholefield dynamic-fringe patterns provide a basis for simultaneously observing the interaction between propagating cracks and the stresses which drive these cracks. Fracture Control Experiments Improvements in the efficiency of the drill and blast procedures must involve close control of the fracture process following the detonation of an explosive charge in a bore hole. By control it is implied that the number of cracks initiated and the location of each crack on the wall of the bore hole can be specified. Control also, involves orienting each crack and maintaining the crack path and velocity until the specified crack length is achieved. If the entire fracture process can be controlled, then rounds can be designed to optimize volume removed. fragment size and minimize costs. One area of blasting where fracture control is vitally important is in underground excavation where the strength and stability of the rock walls must be maintained and smoothness and precision of the walls must be achieved. The smooth blasting method is one of the most commonly employed procedures for achieving some degree of fracture control. In smooth blasting, the central region of material is first removed, and then the final row of closely spaced undercharged or cushioned holes are fired to remove the final volume and produce a smooth wall. In some instances, unloaded or dummy holes between the loaded holes are recommended to guide the fracture plane. This investigation pertained to an evaluation of 3 features of the smooth blasting process. These included (a) the effect of stress reinforcement on fracture by simultaneously firing 2 charges; (b) the influence of a dummy hole on control of the fracture planes between 2 simultaneously fired charge holes; and (c) the influence of dummy hole spacing on fracture plane control.

Jan 1, 1979

By W. H. Patnode

The effect of suspended solids on the resistivity of slurries is discussed and the relationship between drilling mud resistivity and mud filtrate investigated. It is concluded that it is erroneous to substitute mud resistivity for mud filtrate resistivity in electric log calculations. A recommendation is made that both the bud resistivity and the mud filtrate resistivity be determined when electric logs are run. INTRODUCTION The electric log is influenced not only by the resistvity of the drilling mud in the borehole at the time of logging but also by the resistivity of the drilling mud filtrate. Sherborne and Newtoni investigated the relationship of mud resistivity to mud filtrate resistivity and concluded that, "The resistivity of the mud in most cases closely approximates that of its filtrate," and "In fact, with the exception of Aquagel and its filtrate, the figures for any particular mud and filtrate are almost identical." Present practice is to determine only the drilling mud resistivity and apply this same value to calculations involving the mud filtrate. The purpose of this study is to reexamine the factors governing the relationship between mud resistivity and mud filtrate resistivity. EFFECT OF BOREHO1.E FLUID ON THE ELECTRIC LOG Resistivity Log The resistivity log may be modified by the resistivity of the borehole fluid in two different ways: (1) The apparent resistivity of a for-formation may be different from the true resistivity of the formation because of the flow of some current through the drilling mud in the borehole. Therefore the resistivity of the mud is an important factor. (2) The apparent resistivity may differ from the true resistivity, if a formation is invaded by mud filtrate, because of displacement by the mud filtrate of some of the interstitial fluid in the formation. In this case the resistivity of the mud filtrate rather than the resistivity of the mud is the important factor. Self Potential Log The self potential arises, in part, from electrochemical effects resulting from the interaction of connate waters in porous formations and the fluid in the borehole. Expressed in simple form, E = Klog-p where E is the electrochemical self potential, K is a derived constant, pl is the resistivity of the borehole fluid, and p2 the resistivity of the water in the formation. A theory of the electrochemical component of the self potential in boreholes has been recently set forth by Wyllie.3 In the above equation resistivities have been substituted for activities of the ions in the fluids.' It is therefore apparent that the resistivity of the mud filtrate is more nearly representative of the activities of the ions than is the resistivity of the mud. However, it is possible that in some instances the ionic activities of cations from certain clays may contribute to the total cationic activity of the drilling fluid to such an extent that the mud resistivity is more nearly representative of the activities than the filtrate resistivity. This is particularly the case when the resistivity of the mud is less than the resistivity of the mud filtrate. In addition the apparent self potential may be influenced by the resistivity of the drilling mud because of current flow through the borehole. RESISTIVITY OF SLURRIES Aqueous drilling muds are slurries containing fine-grained solid particles. The solid constituents consist mainly of added clays and weighting materials in addition to solids contributed by the drilled formations. The filtrate is primarily water in which quantities of salts or other chemicals are dissolved. The resistivity of the fiiltrate is a function of the type and quantity of dissolved material whereas the resistivity of the mud is a function of the combined resistivities of the filtrate and the resistivities of the suspended solids. Experiments have been carried out to determine the relationship between the resistivity of solutions and the quantity and type of solid matter insus-pension. Solid materials of high resistivity, as well as solid materials of relatively low resistivity, have been used. The data obtained make possible the evaluation of the probable effect of suspended solids on the resistivity of drilling mud. Procedure Resistivities were determined by means of a conventional conductivity cell with platinized-platinum electrodes. Total resistance between the electrodes was measured by Kohlrausch's alternating current bridge method using a General Radio Company Type 650-A impedance bridge with telephone. The cell was standardized with potassium chloride solutions of known normalities in order to calibrate the cell so that measured resistances of slurries could be converted to resistivities. Resistivities were determined for mixtures of potassium chloride solution and solid materials by placing a measured quantity of solution in the cell and adding weighed quantities of solid materials in small increments to the solution. The net change in resistance on addition of solid materials was measured. Even distribution of the solid particles was maintained within the cell by a motor-driven glass propeller before measurements were made. Slurries Containing High-Resistivity Solids Powdered silica sand having a maximum diameter of about 60 microns and precipitated chalk of commercial grade were used to make the slurries whose resistivities were measured. Both of these substances have high resistivities, are virtually insoluble, and effectively do not carry current in a slurry. The resistivities of slurries composed of potassium chloride solution and these two solid materials are given in Table 1. The ratio of the resistivity of the solution to the resistivity of the slurries was computed and was found to follow the relationship established by Archie

Jan 1, 1949

By W. H. Patnode

The effect of suspended solids on the resistivity of slurries is discussed and the relationship between drilling mud resistivity and mud filtrate investigated. It is concluded that it is erroneous to substitute mud resistivity for mud filtrate resistivity in electric log calculations. A recommendation is made that both the bud resistivity and the mud filtrate resistivity be determined when electric logs are run. INTRODUCTION The electric log is influenced not only by the resistvity of the drilling mud in the borehole at the time of logging but also by the resistivity of the drilling mud filtrate. Sherborne and Newtoni investigated the relationship of mud resistivity to mud filtrate resistivity and concluded that, "The resistivity of the mud in most cases closely approximates that of its filtrate," and "In fact, with the exception of Aquagel and its filtrate, the figures for any particular mud and filtrate are almost identical." Present practice is to determine only the drilling mud resistivity and apply this same value to calculations involving the mud filtrate. The purpose of this study is to reexamine the factors governing the relationship between mud resistivity and mud filtrate resistivity. EFFECT OF BOREHO1.E FLUID ON THE ELECTRIC LOG Resistivity Log The resistivity log may be modified by the resistivity of the borehole fluid in two different ways: (1) The apparent resistivity of a for-formation may be different from the true resistivity of the formation because of the flow of some current through the drilling mud in the borehole. Therefore the resistivity of the mud is an important factor. (2) The apparent resistivity may differ from the true resistivity, if a formation is invaded by mud filtrate, because of displacement by the mud filtrate of some of the interstitial fluid in the formation. In this case the resistivity of the mud filtrate rather than the resistivity of the mud is the important factor. Self Potential Log The self potential arises, in part, from electrochemical effects resulting from the interaction of connate waters in porous formations and the fluid in the borehole. Expressed in simple form, E = Klog-p where E is the electrochemical self potential, K is a derived constant, pl is the resistivity of the borehole fluid, and p2 the resistivity of the water in the formation. A theory of the electrochemical component of the self potential in boreholes has been recently set forth by Wyllie.3 In the above equation resistivities have been substituted for activities of the ions in the fluids.' It is therefore apparent that the resistivity of the mud filtrate is more nearly representative of the activities of the ions than is the resistivity of the mud. However, it is possible that in some instances the ionic activities of cations from certain clays may contribute to the total cationic activity of the drilling fluid to such an extent that the mud resistivity is more nearly representative of the activities than the filtrate resistivity. This is particularly the case when the resistivity of the mud is less than the resistivity of the mud filtrate. In addition the apparent self potential may be influenced by the resistivity of the drilling mud because of current flow through the borehole. RESISTIVITY OF SLURRIES Aqueous drilling muds are slurries containing fine-grained solid particles. The solid constituents consist mainly of added clays and weighting materials in addition to solids contributed by the drilled formations. The filtrate is primarily water in which quantities of salts or other chemicals are dissolved. The resistivity of the fiiltrate is a function of the type and quantity of dissolved material whereas the resistivity of the mud is a function of the combined resistivities of the filtrate and the resistivities of the suspended solids. Experiments have been carried out to determine the relationship between the resistivity of solutions and the quantity and type of solid matter insus-pension. Solid materials of high resistivity, as well as solid materials of relatively low resistivity, have been used. The data obtained make possible the evaluation of the probable effect of suspended solids on the resistivity of drilling mud. Procedure Resistivities were determined by means of a conventional conductivity cell with platinized-platinum electrodes. Total resistance between the electrodes was measured by Kohlrausch's alternating current bridge method using a General Radio Company Type 650-A impedance bridge with telephone. The cell was standardized with potassium chloride solutions of known normalities in order to calibrate the cell so that measured resistances of slurries could be converted to resistivities. Resistivities were determined for mixtures of potassium chloride solution and solid materials by placing a measured quantity of solution in the cell and adding weighed quantities of solid materials in small increments to the solution. The net change in resistance on addition of solid materials was measured. Even distribution of the solid particles was maintained within the cell by a motor-driven glass propeller before measurements were made. Slurries Containing High-Resistivity Solids Powdered silica sand having a maximum diameter of about 60 microns and precipitated chalk of commercial grade were used to make the slurries whose resistivities were measured. Both of these substances have high resistivities, are virtually insoluble, and effectively do not carry current in a slurry. The resistivities of slurries composed of potassium chloride solution and these two solid materials are given in Table 1. The ratio of the resistivity of the solution to the resistivity of the slurries was computed and was found to follow the relationship established by Archie

Jan 1, 1949

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By L. J. M. Smits

A theoretical equation is developed describing membrane potentials of shaly sands as a function of the cation-exchange capacity per unit pore volume of the rock and saturating water salinity. This equation is based on the same simple physical model as that employed earlier7 describing the electrical conductivity of shaly sands. Experiments conducted with NaCl solutions showed that the equation is obeyed, except in the case of saturated salt solutions where minor deviations were observed. A possible explanation is given for this discrepancy. As the clay content and the porosity of shales may vary appreciably, shale membrane potentials also vary. It was found that membrane potentials of shales can be calculated accurately with the aid of the same theory. Consequently, changes in membrane potentials can be accounted for by simple measurement of cation-exchange capacities per unit pore volume of both shales and shaly sands. Charts are given to facilitate interpretation of the electrochemical part of the SP in terms of cation-exchange capacities and the salinities of mud filtrate and formation water. INTRODUCTION A spontaneous potential (SP) log is a record of the way in which the electrical potential of a sonde varies as it passes down a borehole. Such variations frequently reflect rock texture, e.g., permeable beds intercalated in an impermeable series often are indicated by a sharp change in potential. Nowadays it is recognized that SP logs may be interpreted in terms of formation-water salinity and formation shaliness. The four sources of the SP are illustrated in Fig. 1. El and E4 represent streaming potentials generated by the flow of mud filtrate through mud cake opposite permeable formations and through shale, respectively. An extensive review of the literature on the evaluation of these streaming potentials is given by Lynchl and will not be discussed here. The remaining part of the SP generally is called the electrochemical potential, which is divided into two parts: a membrane potential across the shale (E3, Fig. 1) and a membrane potential in the permeable sand at the diffusion boundary between formation water and mud filtrate (E2, Fig. 1). It was found by wyllie2 that the membrane potential across the shale, E3, is the most important contribution to the electrochemical potential, the shale acting as a semi permeable membrane. When the sand is clean it does not influence the diffusion process, so E2 equals the value of the so-called liquid-liquid junction potential observed when the two solutions diffuse freely into each other. When the sand contains clay, however, this interferes with the diffusion process and affects the diffusion potential generated. The greater the proportion of clay, the stronger this effect will be. Wyllie,3 Doll4 and Poupon et al.5 took this effect into account theoretically, starting from a physical

Jan 1, 1969

By M. E. Fine, A. A. Hendrickson

The critical resolved shear stress and the strain rate dependence of the .flow stress are reported for Ag base A1 single crystals up to 6 at. pct A1 over a temperature ralzge of 4.1° to 470°K. At room temperature the solid solution strengthening is attributed brinciballv to an increase in the dislocation density on alloying. At 42°K the alloys are relatively stronger because the dislocations widen on alloying and are more difficult to cut. In a previous paper, the authors reported the characteristics of strain aging in Ag base A1 alloys.' The variation of the magnitude of the strain-aging yield drops on aging time, aluminum content, and testing temperature strongly indicated that the phenomenon is due to the Suzuki mechanism. In the present paper, the critical resolved shear stress (CRSS) and the strain rate dependence of the flow stress are reported for Ag base A1 single crystals as functions of testing temperature (4.2" to 470") and A1 content (0 to 6 at. pct). Observations on the substructure and measurements of the effect of crystal growth rate are also given. The experimental re- sults appear explainable considering that aluminum additions increase the dislocation density and dislocation width. EXPERIMENTAL METHOD The methods of specimen preparation and tensile testing were described previously.' Briefly, single crystals were grown from the melt in a vacuum (1 x lom5 mm Hg), shaped into tensile samples by a combination of abrading and acid etching, annealed at 850°C in a vacuum (1 x 10" mm &Z) for several days, and furnace cooled to 200'. The testing was done on a model TM Instron using friction grips and a strain rate of about 5 x 106 per sec unless otherwise noted. The various testing temperatures were obtained by immersing the specimens in the following media: 1) 4.2': liquid helium using the apparatus of G. Byrne;' 2) 77°K: liquid nitrogen; 3) 200"K: dry ice and acetone; 4) 415' K: ethylene glycol; 5) 460' \ to 480' : molten Stanalax. In the determination of the CRSS above 296' K, a ratio method was used; the crystals were strained initially at the higher temperature, 0.1 pct shear strain, and then tested at 296' . The ratio of the flow stress between the two temperatures was then multiplied by the average CRSS at 296' K to obtain the value of the CRSS at the high temperature. (The test at 296' showed a yield point resulting from strain aging; the flow stress at 296' K was taken as the lower yield stress.) The ratio method, we believe, is more accurate than using different crystals since

Jan 1, 1962

By John S. Johnson

The maintenance cost, or renewal cost, in any preparation plant is a large item of expense and reflects in the total cost of producing and preparing the ton of coal. It is given constant study to the end that ways and means of controlling and reducing this proportion of the total cost may be developed. Study of this item of cost has proceeded along usual lines, which are: proper functioning of the maintenance organization; systematic and thorough inspection to prevent breakdonns; the making of repairs before renewals are needed; maintenance work done thoroughly the first time, instead of patching, study of parts needing frequent renewal or repairs or conditions resulting in delays, thorough knowledge of cost by the mall responsible for maintenance; and the use of special equipment and materials. This paper is to deal with special equipment and materials to reduce the maintenance cost hut before going into that I want to express an opinion on the general subject. Maintenance Organization Usually maintenance is taken care of by a group of men who perform their work on the off shift. The work is arranged by the operating official who should be thoroughly familiar with maintenance, so that materials needed may be made up for the particular job and waste of time in looking up materials be prevented. To perfect the maintenance organization, all operating attendants should be thoroughly trained to be familiar with all working parts of their equipment, to make a thorough inspection and to write out the slip for the work required. This requires job analysis, but it is worth the effort, because the attendant usually is better informed than anyone else about his particular equipment. The operating official can judge the scope of the work to direct the repair and to have material ready. Lubrication is an important item in maintenance, and a subject by itself. Usually the breaker oiler is designated to perform this task. This man should be picked for his ability and put in line for promotion to machinist. He should be trained as an inspector, as he is constantly visiting most parts of the breaker and has an opportunity to observe needed maintenance. The first thing is to lay out maintenance work and arrange to have it done; the next is to check the work and see that it has been properly done. This check should be made by the operating official, and through the attendant. The cost statement showing the various items of maintenance cost is not often understood by the man in direct charge. Cost sheets should be simplified and worked up by breaker sections; e.g., the cost of

Jan 1, 1947

By John S. Johnson

The maintenance cost, or renewal cost, in any preparation plant is a large item of expense and reflects in the total cost of producing and preparing the ton of coal. It is given constant study to the end that ways and means of controlling and reducing this proportion of the total cost may be developed. Study of this item of cost has proceeded along usual lines, which are: proper functioning of the maintenance organization; systematic and thorough inspection to prevent breakdonns; the making of repairs before renewals are needed; maintenance work done thoroughly the first time, instead of patching, study of parts needing frequent renewal or repairs or conditions resulting in delays, thorough knowledge of cost by the mall responsible for maintenance; and the use of special equipment and materials. This paper is to deal with special equipment and materials to reduce the maintenance cost hut before going into that I want to express an opinion on the general subject. Maintenance Organization Usually maintenance is taken care of by a group of men who perform their work on the off shift. The work is arranged by the operating official who should be thoroughly familiar with maintenance, so that materials needed may be made up for the particular job and waste of time in looking up materials be prevented. To perfect the maintenance organization, all operating attendants should be thoroughly trained to be familiar with all working parts of their equipment, to make a thorough inspection and to write out the slip for the work required. This requires job analysis, but it is worth the effort, because the attendant usually is better informed than anyone else about his particular equipment. The operating official can judge the scope of the work to direct the repair and to have material ready. Lubrication is an important item in maintenance, and a subject by itself. Usually the breaker oiler is designated to perform this task. This man should be picked for his ability and put in line for promotion to machinist. He should be trained as an inspector, as he is constantly visiting most parts of the breaker and has an opportunity to observe needed maintenance. The first thing is to lay out maintenance work and arrange to have it done; the next is to check the work and see that it has been properly done. This check should be made by the operating official, and through the attendant. The cost statement showing the various items of maintenance cost is not often understood by the man in direct charge. Cost sheets should be simplified and worked up by breaker sections; e.g., the cost of

Jan 1, 1947

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By E. A. Gulbransen, W. S. Wysong, K. Andrew

INTRODUCTION THE reaction of carbon in solid solution in a metal with the surface oxide film on many metals may be inferred from thermodynamic calculations for high vacua and high temperature conditions. Holm1 has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. Considerable work has been described in the literature on the decarburization reaction. Several general references may be noted.2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides 0n strips of various types of chrome-nickel alloys. Some of the early experiments on the behavior of 13 pct chrome-iron in vacua of the order of 5 X 106 mm and at a temperature of 600°C have been reported.5 These experiments showed a slow reaction with the residual oxygen or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600°C pure enough to reduce Cr203 formed on the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome iron and Nichrome V has been investigated in the thin film range by Gulbransen, Phelps and Hickman,6 and shown to be Cr203. It was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pct nickel and 20 pct chromium was heated to 850°C in a high vacuum, the specimen' lost weight. The rate of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. TYPE REACTIONS Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature, of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type. They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: [I. Metal • (gas) ;--* metal + gas - degassing of the metal 2. xM(s) + y ½ 02(g) tom- M.0„ (s) – oxidation]

Jan 1, 1948

By A. H. Daane, B. J. Beaudry

The Sc-Ti system was studied by thermal, metal-lographic, and X-ray methods. Scandium was found to transform at 1334 °C from a (hexagonal) to ß which was concluded to be bee since a continuous series of solid solutions is formed between ß scandium and ß titanium at elevated temperatures. There is a minimum in the solidus at 51 wt pet Ti and 1300°C, a monotectoid at 1050°C and 49 wt pet Ti, and a eutectoid at 875°C and 91.5 wt pet Ti. The maximum solubility of titanium in a scandium is 13.5 wt pet at the monotectoid temperature, while the maximum solubility of scandium in a titanium is 6.5 wt pet at 875°C. SCANDIUM, a member of Group 111 A of the periodic table, and now called a rare-earth metal,' has become of interest recently due to its low density (2.99 g per cc) and relatively high melting point (1539°C).Spedding,' et al. have described a method of preparation of pure scandium metal and have made a study of its basic properties. Since scandium is approximately 10 to 12 pet smaller in at. diam than the other rare earths while its electronegativity and valence are the same, a knowledge of its alloying behavior in contrast to these elements should be very helpful to fundamental alloy theory. Since scandium is quite scarce and difficult to prepare in pure form, its use as a structural material by itself seems quite unlikely. However, its use in special cases as an alloying addi- tive to other low-density materials is a possible application; the Sc-Ti system was chosen for this reason and for others of fundamental interest. Scandium was suspected of having a high temperature bee form as do some of the other rare-earth metals.3'4 Since titanium has a high-temperature bee form, a continuous series of solid solutions at elevated temperatures between ß scandium and ß titanium would prove the existence and structure of the high-temperature form of scandium. The existence of a continuous series of hexagonal solid solutions at room temperature was predicted by Burkhanov and Savitskiy,5 but Hias shown to be incorrect in early X-ray studies. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar titanium and distilled scandium prepared by the method described by Spedding,2 et al. The major impurities are listed in Table I in PPm. Alloy Preparation. All the alloys examined were initially formed in a nonconsumable electrode are-melting furnace under an atmosphere of purified helium or argon. A curve based on the observed weight loss of 0.6 pet* when titanium was melted

Jan 1, 1962