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By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.''' A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.' In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.''7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961

By Walter Remmers

THE fact that gray iron increases in volume, cracks and distorts upon repeated heating and cooling is rather common knowledge. In ingot molds, Diesel engine pistons, carburizing boxes, continuous furnace parts, grate bars, stoker parts, and all castings that are subjected repeatedly to high and low temperatures, the phenomenon of growth presents a vital problem. Ingot molds distort and produce cracks which result in seams or laps and later appear as defects in the finished product. The heads of Diesel pistons frequently fail by cracking in a stellar shape. This is attributed usually to the result of permanent growth. Distortion and change of dimension of furnace parts frequently renders them entirely unusuable. In chain grate stokers, mechanical difficulties frequently are caused by the growth of the links. In proper operation these links should never attain a temperature sufficiently high to start growth; nevertheless, some have grown 1/8 in. on an 8-in. length when improperly operated. Even though the phenomenon is generally known there still exists a deficiency in the explanation of the mechanism of this growth. The field of investigators of this subject has a decided variation in opinion concerning the causes. The problem is of sufficient importance therefore to warrant further consideration.

Jan 1, 1930

By Ole Singstad

THE legislatures of New York and New Jersey, determined in 1919 that a vehicular tunnel should be built under the Hudson River. On July 1, 1919, an engineering staff was organized with the late Clifford M. Holland as chief engineer, and this staff was given a number of problems to solve, such as location, size, type of tunnel, method of construction, method of ventilation and cost. After a period of preliminary investigations and studies it was decided to build the tunnel at Canal St., New York, connecting 12th St., Jersey City. This is the center of the heaviest traffic across the Hudson River. It was also decided to build two tunnels-one for west-bound traffic and one for east-bound traffic-the tunnels to be of cast iron, built up of segments and bolted together, each tunnel to have a roadway 20 ft. wide and a clear heat room of 13 ft., 6 in. This is to provide for two lines of vehicles in each direction. The tunnels have an exterior diameter of 29 ft., 6 in. The interior lining is of concrete, the sidewalls tiled with a vitreous white tile and the roadways paved with granite block. The entrances and exits at both ends are separated by two blocks so as to reduce traffic congestion. BASIS OF VENTILATION It was recognized very early that one of the most important problems confronting the engineers was a proper ventilation system. It was estimated that each tunnel as planned would have a traffic capacity of 1900 vehicles per hr. The tunnels are 8500 ft. long between portals, and it was considered that the ventilation should be based on all of these vehicles being operated by gasoline engines. That presented a problem in ventilation unlike any other either in magnitude or character.

Jan 8, 1926

Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribution to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While' it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind maybe said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others. In a generic way, metallurgists now speak of carbides, sub-carbides, double carbides, special carbides, and other combinations. It is very desirable that these should be accurately defined and understood. It is also desirable to know whether there are other or new forms; if so, can these be separated and their characteristics obtained. It may be interesting to point out that the carbon compounds now definitely known are stated to number over 80,000. It is very probable, therefore, that there is room for much valuable and useful research to be carried out with the object of increasing our knowledge of the various combinations of carbon with iron, as probably some of these are still unknown

Jan 5, 1914

By V. Rajaram

The oil shales of the Green River Formation in the United States have been considered as a source of liquid hydrocarbons since 1908, with the first retort constructed in Colorado in 1917. However, it was not until 1944 that the mining characteristics of oil shale were investigated in a systematic manner. During the period 1944 through 1956, the Selective Mine and the Demonstration Mine (also referred to as the Anvil Points Mine) were operated by the U. S. Bureau of Mines (USBM) near Rifle, Colorado. Significant progress was made in developing a room and pillar mining method by which oil shale could be mined safely at a very low cost per ton. Mechanical properties of oil shale were determined, safe room spans and roof support techniques were established, and drilling and blasting methods for oil shale were developed. As a follow-on to this USBM effort, a consortium of six oil companies with Mobil Oil Company as project manager carried out a research program during the period 1964-68 at the Mobil mine, located in the vicinity of the Anvil Points mine. Rock mechanics investigations were conducted as a part of this research program, and consisted of laboratory studies, in-situ stress determinations, and roof and pillar instrumentation. This paper will discuss the findings at the Anvil Points mine and Mobil mine to illustrate the stability considerations in underground oil shale mining.

Jan 1, 1983

By N. E. Maccallum

Almost half a century has passed since the Siemens brothers, after tedious and costly experiments, finally began the manufacture of open-hearth steel. The furnace of that time was very small, having a hearth-capacity of from 3 to 4 tons, and we can appreciate the wonderful development that has taken place in those 50 years by the knowledge that to-day furnaces of 50 times the original capacity are in operation. As the new steel process assumed importance, and furnaces began to grow in number and in size, a question arose, to which no satisfactory answer has ever been given, and that was: aWhat is the safe and economical limit of the open-hearth furnace ?" Various stopping-places have been suggested, and 20, 30, 40, and 50 tons have each been advocated, but all such arbitrary restrictions have been passed, and 60 tons would probably represent the average furnace, although in a few instances from 70 to 80 tons are regularly tapped into one ladle. The furnaces which are the subject of the present paper have gone far beyond even these limits, and since, in my opinion, they mark another step in the progress of open-hearth steel, they will be considered fairly and frankly, in order that those to whom the matter may be of interest may be able to judge and form their own conclusions. Short accounts of the work of these furnaces have appeared from time to time in various technical journals, of which the following is a brief résumé. These furnaces are the property of the Phoenix Iron Go., of Phœnixville, Pa., and their distinctive and important feature is, that they charge to twice the capacitl of one ladle, and tap simultaneously into two ladles, with a device for controlling the flow into either. In this way the capacity of the furnace is not limited, as formerly, but heats of any size within the capacity of two ladles may be charged.

Jan 1, 1913

By Charles J. Potter

There are many sources of energy available for consumption. Some available are solar, tide and wind. However, in terms of relatively large usage, only four principal sources are used for primary energy today. They are coal, oil, natural gas and water power. Such additional items as wood and nuclear energy, although supplying quantities of energy today, do not in the aggregate amount to any real significant quantity, but nuclear energy must be considered for future use. In addition, such a thing as gas from distillation of coal and oil is not considered primary energy. The principal markets for primary energy are the electric power utilities, space heating, industrial uses and transportation. The electric utility use of energy is primarily from coal, followed by natural gas and water power. Space heating is primarily a gas market, followed by oil and then coal. Space heating by electricity is only considered in the generation of electric power. Transportation's principal source of energy is oil. Coal has practically no market left in this field.

Jan 4, 1962

By W. E. Wrather

The overproduction of crude oil in 1927 has received such widespread publicity, both within and without the industry, and the several factors which have brought about this situation are so thoroughly agreed upon by everyone, that it is unlikely the writer will in this brief review be able to contribute anything new. The entire story of low prices and demoralization revolves around two flush districts, Seminole and West Texas— the actual. performance of Seminole and the potential threat of West, Texas. The sustained production of California has been a contributing factor to this situation also. It seems reasonably certain that Seminole and West Texas will together dominate the industry during 1928, with Seminole probably destined to drop into second place, as additional pipe lines are completed into West Texas to care for its rapidly expanding production. It now appears inevitable that the production of 1928 will equal or exceed that of the past year, depending solely upon the rapidity wit,h which it is possible to market West Texas crude, and the degree of restraint which operators are willing to impose upon themselves in holding proved reserves of oil underground. Adversity has cultivated the growth of a promising spirit of cooperation which has accomplished practical results both at Seminole and in West Texas. Cooperation among oil producers has long been ardently hoped for, but prior to the past year it has never been effective on an important scale. The interests both of the industry and the public at large can best be conserved by cooperation in controlling production, and the widespread acceptance of this idea has paved the way for a more rational policy in the immediate future Production BY Major Districts The domestic production of the United States during 1927 amounted to 894,43.5,000 bbl. (Bureau of Mines), an increase over 1926 of approximately 128,000,000 bbl. California succeeded in maintaining its position of the past four years at 230,000,000 hbl. In 1923 with the Los Angeles

Jan 1, 1928

By W. R. Ingalls

THE paramount subject of interest and concern at the present time is the readjustment in economic conditions following the cataclysmic disturbance produced by the war and the misconceptions leading to an orgy of extravagance that prevailed during two years following the armistice he, time is too short for me to undertake to review the nature and extent of the upheavals occurring between August, 1914, and October, 1920. Bulky volumes will be written about them. . But I shall have to refer to some of the results in order to outline a prognosis. It is the future, not the past;' that is of most interest to us. Let me be so bold as to say, without further preface, that I am not optimistic as to the near future. .We shall, indeed, have revivals in trade, but they will be delusive if their nature be not 'understood. We shall build hopes and expectations upon political maneuvers and events, only to find in the end that they were folly. In the meanwhile fundamental economic influences will continue to exert their steady and irresistible pressure. The new administratiow at Washington has no magic wand with which to kindle the fires in our idle steel furnaces, or create a million new houses for the people; nor can the premiers of Europe put into motion the spindles of the cotton and woolen mills, or by any incantations compel the people of the Orient to buy goods. The people of the Orient, and of, Europe, and of the two Americas are in the grip of the same economic forces. The readjustment has proceeded further in some parts of the world than in others. In the United States I do not think we, have gone more than over the threshold. I shall tell you why 1 think thus, but in telling you I shall be limited, in view of the immensity of the subject, to a series of bald statements, without much elucidation.

Jan 1, 1921

By B. Paul, C. C. Fu

Experiments indicate that the fatigue limit of various drill steels becomes vanishingly small in the presence of water and other corrosive liquids. Therefore one must generally expect fatigue failures of drill steels in a great many field operations. However, it is theoretically possible to so choose the hammer impact speed of a percussion drill in order to maximize the total length of hole drilled before failure occurs. In this paper the existence of an optimum speed is demonstrated and it is shown to be comparable to presently used piston speeds. The influence on drilling speed and hole length of a number of other pertinent design features, such as bit geometry, hammer geometry and steel properties is also established. Although machinery should be designed to obtain optimum performance, it is not always clear just what performance characteristic is to be optimized. For example in a rock drill it would be desirable to optimize all of the following characteristics: drilling speed, bit life, steel life, total length of hole drilled before failure, and efficiency of energy conversion. The word failure could signify excessive bit wear, bit fracture, steel fracture, or some other type of component failure. It is not possible in general to optimize all performance criteria simultaneously. For example, one could achieve fantastically large drilling rates at the expense of bit or steel life, energy requirements and physical size of system. It therefore becomes necessary to compromise requirements in order to achieve a well-balanced albeit non-optimum design. It is, however, extremely useful to explore the interrelationships between the different performance characteristics. Such a procedure would help to establish theoretical limits of performance within the framework of existing knowledge and also serve as a practical design procedure for special applications where a particular performance characteristic is of greatest concern to the user (e.g., steel breakage might be especially undesirable in certain locations). It is the purpose of this paper to examine the problem of how one may drill the deepest possible hole before breakage of the drill steel occurs. Of course the problem is almost trivial if a well defined fatigue limit (endurance limit) exists for the drill steel. In such cases one merely keeps the piston impact speed sufficiently low to insure that the stresses in the steel never exceed the fatigue limit, thereby achieving an infinite life. If, however, no definite fatigue limit exists, as seems to be the case in the presence of even mildly corrosive agents such as water (see later discussion), then a finite life is inescapable and one can at best hope to maximize the useful life of the system. Indeed it will be shown that the system life is related to drilling speed in the manner shown schematically in Fig. 1-a. Even if a definite fatigue

Jan 1, 1965

By AIME AIME

FOR the development of a mine, a shaft of small cross-section is usually sunk, of no larger size than is absolutely necessary. After the mine has been developed and put on a production basis it is a common practice to sink a shaft of larger cross-section for hoisting and use the original shaft for the handling of men and material into the mine. While that ar¬rangement is usually expedient, the small size of the supply cages presents a problem in the handling of ma¬terial. Where a cage is, say, 4 by 4 ft., which is not an uncommon size, all lengthy and bulky material must be handled piece by piece several times from the supply department to the underground stations. Thus drill steel and timbers over 4 ft. long will be loaded on cars at the supply department and wheeled to the shaft, where each piece must be unloaded from the cars and stood up in the cage. They are then lowered to the shaft station, unloaded piece by piece and placed in cars, run to the supply station and again unloaded and stored until called for. In such a case handling becomes a major item in the cost of supplies.

Jan 1, 1930

By R. M. Brick, Arthur Phillips

The normal method of preparing metallic alloys for commercial use involves the preparation of a melt containing the given components in the chosen proportions and allowing the homogeneous liquid mass to solidify in a mold of the desired form. The solidification is frequently accompanied by a segregation of the alloying elements in different parts of the casting. When the segregation is occasioned primarily by marked differences in density of the solid and liquid phases, it is termed "gravity" segregation. When the segregation conforms to a selective freezing in harmony with the teachings of the equilibrium diagram of the alloy system—i.e., the lower melting phases are concentrated in the regions of the casting last to freeze—it is often referred to as "normal" segregation. However, in many cases the lower-melting part of the system is concentrated in the parts of the casting first to freeze and the result in this case is termed "inverse" segregation. To complete the terminology of the subject, normal segregation in a single phase is usually called "coring" and the word will be used in that sense in this paper. Inverse segregation, particularly when the liquid phase is exuded or sweated out on the surface of the casting, is sometimes called "liquation." Unfortunately, some ambiguity has arisen from the use of this term and it is perhaps advisable to confine its use to the dictionary definition; namely, "The separation of two phases by heat sufficient to melt one but not the other." The gravity and normal types of segregation are both well understood and to some extent, are controllable by taking advantage of the most favorable cooling rate for a given casting condition. Inverse segregation has received considerable attention from several investigators but none of the theories offered seem to account in a convincing way for the many examples of this type. The observations made in the present work on segregation in single crystals, and in some other castings, tend to support one theory of the mechanism of inverse segregation and definitely to

Jan 1, 1937

By M. J. Coolbaugh

Mining potash at depths of 3000 ft or more beneath thick water-bearing sediments in Saskatchewan presented a unique challenge to the North American mining industry. Potash is known to flow under pressure, but the knowledge of its flow characteristics at great depths was inadequate for safe design of mine workings and for assured protection from water above the salt formations. At the 3000-ft. depth of the Canadian mines, the potash is stressed beyond its elastic limit, and therefore mining design must deal primarily with its behavior as a plastic material. Recognizing that careful study would be required in order to assure safety and stability of mine workings in deep potash, IMC initiated an extensive rock mechanics investigation of structural properties of potash and salt under high-stress conditions. This presentation consists of a brief review of the development of some methods of testing potash in the laboratory and in the field; some of the rock mechanics concepts and principles derived; and their application to potash mine design. The mining of potash more than 3000 ft beneath the water-bearing sediments in Saskatchewan presented the unique challenge of designing stable mine workings and assuring protection from overhead water in a material that was believed to flow plastically, but whose behavior as a plastic material was not sufficiently known. Under the stress conditions ordinarily encountered in mining, most rocks behave as elastic materials; that is, they compress slightly under pressure, and rebound when the pressure is released. Salt and potash, however, are different. Even under the relatively low pressures encountered at shallow depths, these materials become slightly plastic and yield to stress by flowing.* The plastic properties become more pronounced at greater depth and pressure, and the question arises as to whether or not the plastic flow will be rapid enough and exert enough pressure to destroy underground structures or interrupt the mining process. It was found, however, that not only was there an insufficiency of information about the behavior of potash and salt, but conventional methods of testing these materials, such as determining the modulus of elasticity, Poisson's ratio, and uniaxial compressive strength, were inapplicable because of the high stress conditions prevailing at the 3000-ft depth. Potash under high pressure, for example, has practically no modulus of elasticity, its stress-strain relationship varies with time, and its compressive strength depends upon the degree of confinement. Elasticity and Stress/Strain Relationship: Fig. 1 shows a standard stress/strain chart for potash as made by the Department of Mines in Canada. Typically, when stress is applied to a hard-rock specimen, the specimen contracts, then expands to its original shape when the stress is withdrawn. This chart illustrates, however, that potash under stress yields to the stress by flowing, and does not expand when the stress is withdrawn. When the applied stress was held constant for 30 min, beginning at points A and C, the strain continued to increase and the potash flowed to points B and D, respectively. Points B, D, F, and H show that the potash did not return to its original shape when the stress was released. Thus it can be observed that potash has practically no elasticity and that the amount of strain depends upon the length of time that the stress is applied. Compressive Strength: The conventional method of determining the compressive strength of hard material is to find the maximum pressure that long slender specimens of the material can withstand without failing. As illustrated in Fig. 2,* line B, a standard 2-in. cube of potash subjected to a conventional type of uniaxial compressive test will exhibit a strength of about 5000 psi. However, the compressive strength exhibited can be made to change by changing the conditions under which the test is made. For example, if teflon plates lubricated with graphite are inserted between the press and the specimen, thus minimizing end constraint, the compressive strength is only about 2500 psi, shown in line A. If a specimen is cut in half, changing the width-to-height ratio to 2 : 1 instead of 1:1, and then tested without lubri-

Jan 1, 1968

By S. Chander, D. W. Fuerstenau

The inherently sluggish nature of the reactions involving sulfide minerals, particularly molybdenite, in aqueous solutions under ambient flotation conditions make their investigation complicated and difficult. Since the physicochemical nature of sulfides is known to be controlled by electrochemical reactions, a number of attempts have been made in the past to study sulfide mineral-collector interactions through rest potential and electrode polarization measurements. The purpose of the present investigation was to study the interaction of potassium diethyldithiophosphate (KDTP) with molybdenite. In the present investigation of the interaction of KDTP at the molydenite surface, molybdenite electrode rest potential measurements and electrode polarization behavior were experimentally determined under various solution conditions. The standard reduction potential for the equilibrium between dithiophosphate ions (DTP-) and bis(diethoxythiophosphoryl)disulfide (DTP) [(DTP). + 2e :i7-± 2DTP- (1)] can be evaluated from the electrode rest potential measurements on a platinum electrode in deoxygenated KDTP solutions saturated with freshly prepared (DTP)2. Experimental A platinum wire was used as the electrode for potential measurements. Prior to each measurement the elec-

Jan 1, 1975

By G. T. Hahn, C. N. Reid, A. Gilbert

An evaluation is made of the possible cautsal relationship between twinning and fracture in molybdenum. For both single and poly crystalline material no instance of twin-induced fracture was observed. Instead brittle fracture was found to be slip-induced at heterogeneities. For single-crystal material, the yield stvess in compression and the fracture stvess in tensiow obey a similar angular- relationship which follows approximately a 1/cos2 ? law. where 0 is the angle between the specimen axis and the nearest (100) plane. This sittlilarity between yield and fracture behavior casts doubt on the interpretations made previoltsly that a 1/cos2? relationship supports a critical normal fracture stress criterion. SINCE fracture in brittle materials takes place at stresses an order of magnitude lower than the theoretical strength of the lattice, it must be postulated that some stress-concentrating effect is operative during the fracture-initiation process. Several mechanisms have been proposed whereby the necessary stress concentrations could be produced. The well-known Cottrell mechanism1 describes a dislocation interaction which can lead to the formation of an incipient cleavage crack on a cleavage plane, and both zener2 and stroh3 have discussed models which predict the stress concentration at the intersection of a slip band with a grain boundary. When twinning occurs twin/twin intersections and twin/grain boundary intersections represent another possible means of fracture initiation. Although still controversial, the concept of twin-induced fracture is supported by a weighty mass of evidence, which has been reviewed in a recent paper.4 This investigation was conducted in order to assess the extent to which the brittleness of molybdenum can be ascribed to this cause. Emphasis was placed on seeking direct metallographic evidence for twin-induced fracture such as arrangements of twins located at the fracture origin. EXPERIMENTAL PROGRAM Materials. The experimental materials are described inTable I. From the chemical analyses and estimates of the amounts of interstitials likely to be retained in solution,5 it is concluded that all were mul-tiphased systems. X-ray diffraction experiments6 showed no evidence of preferred orientation in the polycrystalline materials. Single crystals were grown from Molybdenum X and Y using the floating-zone technique,' in a vacuum of better than 3 x 10-5 Torr. However difficulties were experienced with Molybdenum X due to violent gas evolution from the molten zone, and additional crystals (Crystals 3 to 6) were produced by annealing for 5 1/2 hr at 2300°C under a vacuum of 10-4 Torr. Techniques. A series of tension, compression, and bend tests was conducted. Tension tests were used to demonstrate brittle behavior, to measure brittle-fracture stresses, and to provide fractured specimens for metallographic inspection. Compression tests were employed in order to obtain some ductility and a measure of the yield stress. Furthermore, it was considered that compression loading would permit the study of crack nucleation in the absence of propagation. The bend tests were conducted to facilitate identification of the fracture origin, which would be expected to be at, or near, the tensile surface of the sample. Tests were carried out at temperatures between 78" and 298°K attained by means of a liquid-nitrogen evaporator of modified Wessel design.' Specimens were fashioned by mechanical grinding, and, prior to heat treatment, were electropolished at 10 v in a 3:l mixture of ethyl alcohol and sulfuric acid, using a stainless-steel cathode. Except where noted, a strain rate of 4 pct per min was used. All specimens had a gage section 0.75 in. long; diameters of 0.10 and 0.20 in. were adopted for the tension and compression specimens, respectively, the former of single shoulder design, the ends being gripped in split collets with a conical bearing surface. In the bend test, electropolished specimens measuring 0.080 by 0.25 by 1.25 in. were deformed at 78°K by four-point loading. The bending device had spans of 1 in. between the outer and 4 in between the inner fulcra; it was stressed between the compression anvils of the Instron machine at a constant deflection rate. EXPERIMENTAL RESULTS Polycrystals. Tension and Compression Tcsls. It is apparent from Fig. 1(a) that above 170°K fracture of Molybdenum X takes place at stresses equal to or greater than the compressive yield stress whereas

Jan 1, 1967

By Arthur Knapp

THE law of supply and demand is, in general terms, that law which governs the price of any commodity in an unrestricted competitive market. There are several variables which, for the purpose of this discussion, will be defined only as they apply to the petroleum industry: Production: The volume of petroleum that is moved from leases. Stocks: The volume of petroleum that is in the hands of the tank farm and pipeline companies. Inventory: The value of the stocks at the market. Consumption: The indicated delivery of oil to others than those who hold stocks. Demand: The potential absorbing power of the consuming market. Demand is the expression of the needs of the consumer and may depend on the economic value of the oil to the consumer. In times of low prices, the demand is the same as the consumption but during periods of high, prices or deficiency in supply, the demand may be greater than consumption. A general expression of the law is, as follows: Production or consumption Some relation between stocks and or controls price or demand inventory

Jan 3, 1924

By C. S. Chang

PEARL starch, a corn starch prepared with a minimum of alteration, is a good selective depressant for iron oxide minerals.1 From what is known of the complex chemistry of corn starch, there is evidence that it consists of a mixture of saturated giant polymeric molecules, both straight and branch- chained, the constituents consisting of glucose units with hydroxyl radicals as active or polar groups. To add to the existing knowledge of the chemistry of the flotation process, it is desirable to ascertain the effects on the corn starch as an iron oxide depressant when some of the hydroxyl radicals are replaced by other active groups that are common to flotation reagents. The ideal way to carry out this investigation would be to test reagents containing different active groups derived from corn starch. The preparation should be such that the reagents possess the same degree and location of substitution and are ac- companied by little or no degradation of the starch molecules. This, of course, is almost impossible to realize, as it is difficult to control the degree and location of substitution as well as to prevent degradation of the starch molecule during preparation.

Jan 9, 1954

By E. F. Sturcken, J. W. Croach

A grain orientation distribution function, P(u,F), was developed for use in predicting physical properties in oriented metals. Examples are given of the use of the function to predict thermal expansion coefficients in rolled uranium rods and plate. The P(u,F) function was synthesized from X-ray difpaction intensity measurements, Ii, norrnally used to plot inverse pole figures. The symbols u and F specify the angles that the crystallographic axes of the grain make with the normal to the sample surface and P(u, F) gives the number of grains oriented in each direction, (u,F). P(u,F) is obtained from a least squares fit of the Ii to an orthonormal set of spherical harmonic functions. The P(u, F) function was also used to define a quantity, J, which is a measure of the departure of the orientation distribution from unifomzity (or "randomness"). The J parameter may be used to follow, quantitatively, the amount of preferred orientation induced as a function of mechanical working or heat treatment. An example is given of the application of the J parameter to prefevred orientation studies of hot- and cold-rolled uranium rods and hot-rolled uranium plate. Because P(u,F) is derived from relative intensity measurements by the powder diffraction technique, it is applicable to material with large absorption coefficients and/or grain size and is particularly suitable for characterizing the preferred orientation of large numbers of samples such as fuel elenzents for a nuclear reactor. IN general the physical properties of an oriented metal depend on the direction in which the properties are measured. Hence to predict physical properties the grain orientation must be known as a function of the direction of the specimen. The conventional methods of expressing preferred orientation measurements are the pole figure1 and the inverse pole figure.2-8 Both methods are difficult to use for predicting physical propertiess because they are graphical and because they are stereographic projections and hence are not "area-true." In the present report a quantitative orientation distribution function, P(u,F), is synthesized from pole density measurements normally used to plot inverse pole figures. For inverse pole figure plots the pole densities, pi, are obtained by powder dif-fractometer intensity measurements of their reflections from a flat surface of the sample, normal to the direction of interest. Each pole density, pi, represents a single orientation, i, and is proportional to the volume of material with orientation, i; hence a set of pi gives an approximation for the general orientation for the sample direction measured. The expression8'7 for calculating the pole densities, pi, from the diffraction measurements was previously

Jan 1, 1963

By N. Cabrera

IN a recent paper Kuczynski' studied the rate at which the crack between a metallic plane and a spherical particle of the same material is filled up gradually when heated at temperatures near the melting point. If x is the radius of contact between plane and sphere (fig. I), Kuczynski shows experimentally that x5 = At [1] where t is the time. Assuming that the mechanism of transport of matter is the volume diffusion of vacant lattice sites, he is also able to prove Eq 1 theoretically. The constant A contains as a factor the self-diffusion coefficient of the metal and he shows that the values for this coefficient deduced from his experiments yield the same activation energy as that calculated by other methods, which is a confirmation of this point of view. Kuczynski has also considered theoretically the law of growth of x which would be expected if surface diffusion were the important mechanism. He suggests that x should then obey a law of the form x7 = At, and claims to be able to decide the mechanism involved from the observed law of growth., The purpose of this note is to prove this incorrect. On the contrary, when the mechanism is surface diffusion Eq 1 is also obeyed, but with a different constant A. Following Kuczynski, we suppose the bottom of the crack (surface A A) to have an average radius of curvature p. As a result of this curvature the concentration of adsorbed atoms in this surface, n(p) per cm2, will be smaller, and the concentration of vacant lattice sites in the neighborhood, N(p) per cm3, will be larger than the corresponding concentrations, n(w) and N(w), for a flat surface. For all practical cases we can write Thomson's formula in the form n(co)— n(P) N(P)—N(cc) _ 2a-a" n(oo) JV(co) kTp [2] where u is the surface energy of the metal and a the interatomic distance. 1. Let us now consider the mechanism of surface diffusion. We suppose the concentration of ad-

Jan 1, 1951