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By D. K. Deardorff, H. Kato

THE transformation temperature of hafnium from hcp to bcc is 1750° + 20 °C in contrast to previously published values by Duwez and fast2 which are believed inaccurate. The Bureau of Mines determined this value by measuring the temperatures at which a sudden decrease was observed in the electrical resistance of hafnium alloys containing up to 18 at. pct Zr, and then extrapolating the temperatures to 0 pct Zr. Duwez1 previously reported a transformation temperature of 1310°C, obtained by use of a rapid-cooling thermal-analysis technique. Later, Fast2 published a much higher value of 1950° 100°C based upon: a) his own determination of 1690°C for the beginning of the transformation range for hafnium containing 5.7 at. pct Zr, and b) his belief that lattice parameters reported3 for Duwez' hafnium indicated i contained 19 at. pct Zr and that the 1310°C value should be associated with that composition. Russell4 subsequently stated that Duwez and Fast probably were reporting their lattice parameters in different units and reassigned a value of 6.0 at. pct Zr to Duwez' hafnium. If this assumption were true, Duwez' hafnium was of approximately the same purity as Fast's, but his transformation value was considerably lower. The reason for this divergence is not known. Fast's value for hafnium containing 5.7 at. pct Zr agrees well with our data. McGeary5 determined a transformation value of 1660°C by metallographic examination of heat-treated specimens, but the zirconium content of his hafnium was not definitely established. The specimens used in this investigation were 1/8-in.-diam rods 6 1/2 in. long, fabricated by hot-swaging bars cut from arc-melted buttons. These buttons were melted from crystal bar hafnium and crystal bar zirconium. The chief impurity in the hafnium

Jan 1, 1960

By D. O. Hobson, J. O. Stiegler, C. J. McHargue

The effects of alloy composition, deformation temperature, heal treatment, ad inlerstilial contamination on the occurrence of deformation twins were studied. The twinning transition temperature varied with composition and was a maximuni of 140°C for the 40 pcl V composition. Tire remperature range of the transition was very narrow. Alloys of 20 to 70 pet V could he cold-rolled and exhibited profuse twinning. The alloys which did not twin at room temperature (10, 80, and 90 pel V) could plot be cold-rolled. Oxygen additions systematically lowered the transition temperatures for all vanadium contents. The transition temperature for a 30 pet V alloy increased with annealing temperature, apparently due to changes in dislocation density and configuration. Twinning did not nucleate fracture in any specimen in the 20 to 60 pet V composition range. THERE is great current interest in the refractory metals and alloys as structural materials. An important factor in considering the ductile-brittle behavior of such materials is the role of mechanical twinning as a deformation mechanism. Mechanical twins have been observed after deformation at low temperatures or at high loading rates in the pure metals iron,1 vanadium,2,3 columbium,4,5 tantalum,6 Chromium,7 molybdenum,8 and tungsten.9 Binary alloys in which mechanical twins have been observed include: iron with silicon,10 phosphorous," or aluminum;12 and chromium, molybdenum, or tungsten with rhenium.13-17 The increase in low-temperature ductility obtained by alloying the Group VI-A elements with rhenium is very important with regard to fabricability, and there has been considerable effort to understand the so-called '(rhenium effect". Factors suggested to explain this effect include:'' 1) increase in solubility of interstitial impurities with alloying (electronic effect): 2) changes in the nature of grain boundary phases; 3) changes in interfacial energies of grain boundaries and stacking faults: and 4) promotion of twinning. Although an outstanding characteristic of these alloys is the profuse twinning that accompanies low-temperature deformation, most studies of the rhenium effect have been concerned with the other factors. During recent studies of refractory-metal alloys, it was noted that solid solutions of columbium and vanadium exhibited high hardness and strength at room temperature and elevated temperature and, surprisingly, also showed considerable ductility at room temperature and below. These alloys deformed by twinning at room temperature when subjected to slow loading rates. It appeared that the low-temperature ductility resulted at least in part from the relaxation of stresses by twinning in a system where slip is difficult. The reason for enhanced twinning behavior in some bee solid-solution alloys is unknown. There have been suggestions18,19 that, as in fee alloys, the

Jan 1, 1965

By Frank Rieber

THE discovery that strongly magnetic bodies localized near the surface of the earth could be detected by the distortion which they produced in the resultant magnetic field marked the beginning of magnetic surveying methods. From an original ability to detect bodies of magnetic iron ore and the like when located very close to the, surface, these methods have been extended until today they promise to give much information with regard to the structure of such slightly magnetic material as sedimentary rock containing only a very small proportion of iron.1 The recent extensions have been made possible through the development of more delicate instruments, and of methods for their use. From the original compass and dip needle, the design of apparatus has progressed until equipment Is typified by magnetic balances capable of measuring the components of the earth's field to an extremely high degree of accuracy. It seems unlikely that the limit of such instrumental development has been reached. Just as the change from compass and dip needle has enabled the location of relatively minor changes in magnetic materials, so additional developments in the direction of increased sensitivity, as well as in greater dependability and constancy of operation, should reveal positively many slight changes which either escape notice in the present surveys or are so small that they cannot with certainty be separated from uncontrollable errors due to inconstant operation of the equipment. The ability to read smaller and smaller variations does not mean, of course, that deductions as to the causes of these variations will be made as accurately and definitely as -is possible with the more pronounced anomalies.

Jan 1, 1928

Escalating energy costs and tough environmental standards were two major factors affecting the minerals processing area in 1978 For the most part, new startups and research and development initiatives were directed toward improving process dynamics, investigating alternative processing strategy, and lowering unit costs. In the flotation area, the trend to larger machines continued. Scientific investigation of the modeling and process control of flotation was apparent, as was the research and development of new flotation reagents.

Jan 5, 1979

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By R. F. Mehl, C. S. Barrett, A. G. Guy

INTRODUCTION IN the last few years this laboratory has published a series of papers on the mecha¬nism of age -hardening.14,1,6,11,20 Briefly stated it has been proposed that hardening is caused by lattice strains created by lat¬tice coherency between matrix and precipi¬tate; much experimental evidence has been advanced to support this thesis. The system Cu-Be is an attractive one to study. It is a system that exhibits marked age hardening; it ought to be subject to the type of analysis of structural changes hitherto explored and it is a prominent example of "discontinuous precipitation," which, though studied in other cases, 6,20 remains largely unexplained. This research shows that hardening in the Cu-Be system proceeds essentially as proposed earlier.14 Guinier-Preston zones have been observed to form on the {100) planes of the matrix; no transition lattice was found. Aging and overaging were ob¬served to occur most rapidly in the region of discontinuous precipitation-the grain boundary-apparently accelerated there by strain. The Constitution of the Cu-Be System The Cu-Be constitution diagram is shown in Fig I. The structure of the ? phase was determined by Misch16 as of the caesium-chloride type with a lattice con¬stant of 2.598 Å High temperature X ray photograms of 7.2 pct Be alloy made by Kossolapow and Trapesnikow13 led them to conclude that the structure of the P phase is simply disordered body-centered cubic with [ao] = 2.79 Å at 750°C. Previous Work The initial work on the age-hardening of Cu-Be alloys was that of Masing, Dahl, Holm, and Haase. Their numerous papers were published in book form in 1929, sub¬sequently translated.18 The effects of Be content, solution temperature, aging tem¬perature, and cold work on the hardness developed in these alloys were studied. An initial decrease in the electrical conduc¬tivity was observed when strips of a 2.5 pct Be alloy were aged at temperatures from 200 to 350°C; a wire of the same analysis failed to exhibit this decrease when aged at 350°C. A volume decrease of 0.6 pct oc¬curred during aging at 250°C. Microscopic investigations of quenched and aged alloys disclosed a regularly ori¬ented "striping" (ripples) on the a and on the ß grains. In the case of the ß the cause of the striping was held to be decomposition

Jan 1, 1948

By W. M. Weigel

Economic deposits of barite occur in Missouri in two main districts. The most important, the Southeastern or Washington County district, is in the southeastern part of the state, mostly in Washington County with a small extension into the northeastern part of St. Francois County. Roughly, it embraces nine townships or about 200,000 acres and accounts for from 80 to 90 per cent. of the state production. The Central district, is in the central part of the state, includes most of Morgan and Miller counties, and parts of Camden; Benton, Moniteau and Cole counties. The area embraced is much larger than the Washington County district, but the deposits are more infrequent. The location and general area covered by the two districts is shown in Fig. 1. There is another small area in southern Franklin County but so far its production has been of small consequence. It might be considered as a northward extension of the Washington County field. An, area in the central part of Hickory County has also produced a small amount. The outline of the districts as shown indicates the general area in which deposits have been found. The total area covered by deposits of barite is only a small part of this, as, in the Central district especially, there may be miles of supposedly barren areas between ore-bearing areas of an acre or two in extent. The date when barite was first mined in Missouri cannot be definit stated, but the industry probably dates back to about 1860. The occurrence of barite was known long before this, as it was encountered in the lead mines in Washington County and mentioned by several earlier writers." Missouri is reported as producing 8000 tons in 1882 so it is evident the industry was well under way in the seventies in order to have arrived at this substantial production. By 1893 Missouri production had increased so that it ranked with that of Virginia, then the largest producer it increased until in 1914 Missouri accounted for about 65 per cent. of the total United States output.

Jan 1, 1929

By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By William G. Pariseau

Advances in numerical methods of analysis and computer technology during the past decade have brought many formerly intractable ground control problems within easy reach of present day graduate mining engineers. However, the new technology brings with it new problems. The identity of these problems are largely those arising from a lack of familiarity with the capabilities and limitations of the new technology. In this regard, the central problem in ground control planning is the calculation of ground motion associated with mining. The fundamentals of this problem leading to a form suitable for computer programming are therefore reviewed. Solution procedures in the broad sense including the gathering of input data and the interpretation of output are described. Computer program capabilities necessary for ground control analysis are discussed and the steps necessary to implement an analysis are outlined.

Jan 1, 1983

By R. B. G. Yeo

Pronounced isothermal martensite formation at room temperature was measured dilatometrically in a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pctAl, 2.58 pct Ti and 0.25 pct Cb. It is shown that martensite will form isothermally if stabilization of the austenite-martensite transformation is eliminated by removal of carbon. The decarburization of two iron-nickel alloys allows isothermal transformation to martensite to occur at temperatures above their athermal Ms temperatures. In an Fe-22.4 pct Ni alloy, at the 0.008 pct C level, the Ms temperature during air cooling is 85°F higher than that during- water quenching-. At the 0.15 pct C level this difference is reduced to only 5°F. The introduction of carbon causes stabilization during air cooling which lowers the Ms temperature virtually to the same level as determined during mate?. quenching. Thus in the 0.15 pct C alloy, the Ms temperature is almost independent of cooling rate. It is suggested that rival theories of martensite formation should be reexamined in alloys of sufficiently low carbon and nitrogen content to eliminate the complication of stabilization. The Ms temperature of a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pct Al, 1.58 pct Ti and 0.15 pct Cb, solution treated at 1500°F and air cooled as 1/8-in. diam specimens, was found to be 57 °F. 1 However, when held for several hours at room temperature the steel hardened slightly and became appreciably ferromagnetic. Isothermal transformation to martensite was first revealed by Kurdjumov and Maksimova2 in an iron-base alloy containing 0.6 pct C, 6.0 pct Mn and 2 pct Cu. Most of the other studies of isothermal martensite have also been confined to highly alloyed steels which transform at subzero temperatures; for instance, DasGupta and Lement, 3 Cech and Hollomon, 4 Machlin and Cohen,5 Shih, Averbach, and Cohen.6 Averbach and cohen7 noted a rapidly decaying volume increase at room temperature in a steel containing 1 pct C, 1.5 pct Cr and 0.2 pct V. cina8 and Marshall, Perry, and Harpster9 have described the isothermal transformation to martensite at room and subzero temperature in stainless steels. Kurdjumov10 has recently reviewed the subject, noting that the isothermal formation of martensite can be observed only in the temperature range somewhat below Ms or below -50°C. The isothermal formation of martensite may be characterized as follows: 1) It occurs in steels of widely different compositions, the main prerequisite being a low transformation temperature. 2) The transformation occurs by the formation of new plates and not by the growth of old ones. 3) The isothermal transformation is suppresed by stabilization during slow cooling or holding at temperatures near room temperature. However, the factors governing this mode of transformation are still not fully understood. The formation of martensite isothermally suggests an activated process. The early theories of martensite formation did, in fact, utilize classical nucleation concepts. Kurdjumov 11 first proposed the presence of thermally activated nuclei of different sizes and compositions which would grow if they reached critical size during cooling. This treatment was enlarged and developed quantitatively by Fisher, Holloman, and Turnbull12,13 and was later reviewed by the latter two authors.14 Fisher15 associates Ms with a nucleation rate of one per cc per sec. At slightly higher temperatures the nucleation rate is so low that isothermal formation of martensite is not observed in reasonable times. At slightly lower temperatures the nucleation rate is so high that it could not be suppressed by rapid cooling. By judicious use of parameters Fisher 16 was able to obtain good agreement between classical nucleation theory and the incubation times of martensite formation.4 However the application of these principles to martensite formation in iron-nickel alloys15 predicts that an alloy containing about 30 pct (31 at. pet) Ni would not transform. The presence of an Ms temperature at -223° C in an alloy containing 34.1 pct (33 at. pct) Ni led Kaufman and cohen17 to reject the hypothesis of homogeneous nucleation in favor of the reaction path theory originally proposed by Cohen, Machlin and Paranjpe.18 This theory conveniently explains the formation of martensite athermally but becomes labored when dealing with isothermal formation. Kaufman and cohen19 did explain the isothermal activation of embryos by assuming it to be a result of the expansion of their boundary dislocation loops but this treatment predicts an upper temperature limit of isothermal martensite formation.

Jan 1, 1962

By D. J. McAdam

As shown in three recent papers by the author, in two papers by McAdam and Mebs, and in a paper by McAdam, Mebs, and Geil," the technical cohesive strength of a metal, in any particular state as regards mechanical treatment and heat-treatment, cannot be represented by a single stress value, but must be represented by a diagram with the principal stressest as coordinates. Each point on the boundary of such a diagram represents a technical cohesion limit. The technical cohesive strength thus comprises an infinite number of technical cohesion limits, each representing fracture under a specific stress combination. Moreover, neither the yield strength1 nor the ultimate strength can be represented completely by a single stress value, but must be represented by a diagram with the principal stresses as coordinates. All combinations of the principal stresses may be classified in three groups as illustrated by Fig. I. Fig. Ia shows three typical stress combinations with no two principal stresses equal. The magnitude of each principal stress is indicated qualitatively by the length of the arrow. Arrows pointing away from the cube indicate tensile stresses; arrows pointing toward the cube indicate compressive stresses. Typical stress combinations with two principal stresses equal are illustrated in Figs. rb and Ic. Such stress combinations would be produced by subjecting a cylinder to combinations of uniform axial and radial stresses. The uniform radial stress may be resolved into two equal principal stresses. with the mutually perpendicular directions rotatable around the axis of the cylinder. Fig. ib shows stress combinations with Sz equal to The greatest principal stress is in the axial direction, and the stress combination tends to cause either absolute or relative increase in length.* Fig. u shows stress combinations with S2 equal to St. The greatest principal stress is in the radial direction, and the combination tends to cause either absolute or relative decrease in length. The complete representation of either technical cohesive strength, yield strength, or ultimate strength generally requires a three-dimensional diagram. When two of the principal stresses are kept equal, however, the strength of a metal may be represented by a two-dimensional diagram with the coordinates representing the axial and radial stresses.6-II In this paper, attention will be confined almost entirely to stress combinations with two of the prin-

Jan 1, 1945

By N. H. Emmons

An interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at its plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory. Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaccs. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top mas necessary and the engineering force was started on the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of east copper, but the heat was great that the copper bent readily, due to the jarring of its

Jan 1, 1911

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By Kirtley F. Mather

FROM almost every point of view, petroleum was "strategic mineral number one" during the World War that ended in 1945. Even the spectacular advent of the atomic bomb in the final days of the conflict did not displace it from its position of prime importance, although within a few years uranium will almost certainly be the "number one" material in the minds of military strategists, if it is not even now in that position. But both as fuel and as raw material for chemical industries, petroleum will hold the center of the stage for many years to come. Hardly any other substance illustrates so fully the manner in which science and technology may be combined to achieve the utmost success in contributing to human efficiency and comfort. Fundamental to any understanding of the problems implied by my topic

Jan 1, 1948

By Donald A. Brobst

The minerals barite (BaSO4-barium sulfate) and witherite (BaCO3-barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1980 consumed at least 90% of the world's production of 8.8 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The remaining 10% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity filling, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favorable for the discovery of new deposits of commercial value. Witherite is much less common and abundant than barite, although it is more desirable in many ways as a raw material for the production of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir conditions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemically, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite homogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber industry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and linoleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other substances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weigh down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1983

By Henry Mulryan

DIATOMS are microscopic aquatic plants of the order Bacillariaceae. They are unicellular plants with skeletons made up of amorphous opaline silica. The skeletons show highly ornate, complicated geometrical designs. Diatoms live in water virtually everywhere. They are found in clean sea water, brackish water, and fresh-water lakes and ponds. When conditions are right, diatoms propagate by subdivision in huge numbers. Alkalinity, temperature, and the presence of high concentrations of silica in the water largely control diatom life. When the diatoms die the skeletons drop to the bottom of their habitat to form oozes of vary-ing thicknesses. DIATOMITES Diatomite, or diatomaceous earth, is composed essentially of the siliceous remains of the diatoms, although other organic skeletons are also present, especially in sea-water deposits where radiolaria, sponges and silico-flagellates are common. Impurities are generally carbonaceous material, fine-grained silt, volcanic ash and dust, and occasional coarse grains of sand. Diatomites are marine, brackish, or fresh-water, depending upon types of diatoms and their method of deposition.

Jan 1, 1939

The Reconstruction and Research Division of the United States Council of National Defense has, up to date, prepared two reviews on the above subjects: one covers foreign countries and the other covers the activities in the States. These reviews contain information appearing in various Governmental and public periodicals. While the information on foreign countries is necessarily incomplete and fragmentary, its summation is perhaps the most complete work of this kind so far accomplished. The information from the states consists mainly of bills and ordinances introduced in the state legislature, municipal councils, legislature committee reports, programs suggested by governors, and other state and local officials and local organizations It is realized that a good deal of this information will be useful to engineers studying conditions in the various states, and especially to those who want an insight into the general condition in all the states. For instance, the reconstruction problem in each state involving highway, reclamation, buildings, etc., are covered in detail.

Jan 8, 1919

By D. C. Lindley, D. H. Gaucher

The displacement of oil by water in a waterflood project is accomplished by the action of transient viscous, gravitational and capillary forces which drive fluid through interconnecting pore spaces toward production wells. The relative importance of each of these forces to the effectiveness of the displacement and the production history depends on properties of the reservoir itself and the manner in which it is operated. There has been considerable discussion'-3 concerning the importance of these factors and the extent to which they control the performance of individual waterflood projects. No data have been presented, however, to demonstrate the effect on waterflood behavior of variations in rock permeability, water-injection rates and mobility ratios in three-dimensional reservoir systems in which viscous, gravitational and capillary forces are allowed to assume the proper relative influence on fluid flow. Much information relevant to water flooding has been gained from the study of field case histories. But, the complexity of the systems involved, the difficulty of defining geometry and obtaining sufficient data, and the fact that the same reservoir is never flooded twice with the same initial conditions, all obscure the role of process variables such as rate. Further, mathematical calculations of waterflood behavior are restricted at this time by available mathematical techniques to highly simplified situations. Scaled models, however, do offer an approach at the present time to evaluation of the effects of the pertinent variables. Several investigators have predicted prototype reservoir behavior from observations of model waterflood performance under a variety of conditions. Two-dimensional aspects of waterflood pattern efficiency have been investigated by Muskat, Aronofsky, Dyes, et al, raig, et al,' and Rapoport, et al. he effects of gravity segregation, viscous fingering and permeability stratification have also been studied in two-dimensional models. Craig, et al," studied the importance of gravitational forces on frontal displacement in three-dimensional models with wells on a five-spot pattern. This work in- vestigates the tendency for water to segregate in homogeneous reservoirs because of gravity and to under-run the oil for a range of water-inject ion rates. The effects of permeability stratifications were investigated by these authors using miscible fluids to simulate water-channeling through permeable strata in systems of negligible capillary force. In this investigation, a three-dimensional model of a five-spot pattern flood was designed to represent typical prototype conditions, and the sand and liquid properties were selected so that capillary, gravitational and viscous pressure gradients were scaled. It was not, however, possible to achieve exact similitude regarding viscous fingering when the more viscous oil was used. The effects of rock stratification on waterflood behavior were studied by changing both the permeability ratio and the position of the more permeable sand stratum in a two-layered, horizontal model. For each type of stratification, constant-rate floods were performed and the rates were varied, in separate experiments, over a tenfold range. To observe the effect of mobility ratio on flood performance, two series of constant-injection-rate floods were performed on the most highly stratified reservoir at a water-oil viscosity ratio of one.

By W. H. Bassett, C. H. Davis

ALTHOUGH brasses and bronzes have been made for ages, a systematic study of their physical properties has been carried out only during the years of the present century. Among these properties may be included those which are to be detected by means of microscopic examination; in other. words by the science of metallography. The earlier workers in this field, both in this country and abroad, gave their attention to steel. When the senior author explored the situation in 1902, there was little encouragement to be found in undertaking the study of the non-ferrous alloys. A start was made, and the metallography of the brasses and bronzes, as well as of the copper-nickel-zinc alloys developed materially under his direction. Annealing experiments were begun in 1902, and in the succeeding years the effect of temperature, and the influence of previous working, on the grain size of brass were studied. The conclusions so well known and widely published today were largely reached during those earlier years. . In 1905 the first complete annealing series were made. By this it is meant that brass and copper sheet, 5 B & S Nos. hard, was machined into tensile test specimens, then annealed under accurate control for 30 min. at temperatures up to the melting point of the material. Various determinations were made, including tensile strength and elongation in 2 in. There rapidly followed similar series on all of the copper-zinc alloys from 100 to 60 per cent. copper, on the bronzes, cupronickels, and on copper-zinc-nickel alloys. At this point there was published by Grard, in October, 1909,1 the very comprehensive and complete work on the tensile properties of cartridge brass, 90-10 copper-zinc, and electrolytic copper. The excellent photomicrographs in that paper illustrated the changes in structure produced by cold rolling as well as by annealing at different temperatures, but where Grard's work was confined to copper and to two alloys, the investigations in this laboratory have been over the entire fields of the commercial copper-zinc alloys, copper-tin alloys, representative copper-nickel and copper-nickel-zinc alloys as well as aluminum bronzes and others of a more special nature.

Jan 1, 1928

By R. Ehrlich, F. E. Crane

A consolidated porous medium is mathematically modeled by networks of irregularly shaped, interconnected pore channels. Mechanisms are described that form residual saturations during immiscible displacement both by entire pore channels being bypassed and by fluids being isolated by the movement of an interface within individual pore channels. This latter mechanism is shown to depend strongly on pore channel irregularity. Together, these mechanisms provide an explanation for the drainage-imbibition-hysteresis effect. The calculation of steady-state relative permeabilities, based on a pore-size distribution obtained from a Berea sandstone, is described. These relative permeability curves agree qualitatively with curves that are generally accepted to be typical for highly consolidated materials. In situations where interfacial effects predominate over viscous and gravitational effects, the following conclusions are reached. 1. Relative permeability at a given saturation is everywhere independent of flow rate. 2. Relative permeability is independent of viscosity ratio everywhere except at very low values of wetting-phase relative permeability. 3. Irreducible wetting-phase saturation following steady-state drainage decreases with increasing ratio of nonwetting- to wetting-phase viscosity. 4. lrreducible wetting-phase saturation following unsteady-state drainage is lower than fir steady-state drainage. 5. Irreducible nonwetting-phase saturation 101lowing imbibition is independent of viscosity ratio, whether or not the imbibition is carried out under steady- or unsteady-state conditions. Experiments qualithtiveIy verify the conclusions regarding unsteady-state residual wetting-phase saturation. Implications of these conclusions are discussed. INTRODUCTION Natural and artificial porous materials are generally composed of matrix substance brought together in a more or less random manner. This leads to the creation of a network of interconnected pore spaces of highly irregular shape. Since the geometry of such a network is impossible to describe, we can never obtain a complete description of its flow behavior. We can, however, abstract those properties of the porous medium pertinent to the type of flow under consideration, and thus obtain an adequate description of that flow. Thus, the Kozeny-Carmen equation, by considering a porous medium as a bundle of noninterconnecting capillary tubes, provides an adequate description of single-phase flow. With the addition of a saturation-dependent tortuosity parameter in two-phase flow to account for flow path elongation, the Kozeny-Carmen equation has been used to predict relative permeabilities for the displacement of a wetting liquid by a gas. 1-5 It has long been recognized that relative permeability depends not only on saturation but also on saturation history as we11.6,7 Naar and Henderson8 described a mathematical model in which differences between drainage and imbibition behavior are explained in terms of a bypassing mechanism by which oil is trapped during imbibition. Fatt9 proposed a model for a porous medium that consisted of regular networks of cylindrical tubes of randomly distributed radii. From this he calculated the drainage relative permeability curves. Moore and slobod,10 Rose and Witherspoon,11 and Rose and Cleary12 each considered flow in a pore doublet (a parallel arrangement of a small and large diameter cylindrical capillary tube). They concluded that, because of the different rates of flow in each tube, trapping would occur in one of the tubes; the extent of which would depend upon viscosity ratio and capillary pressure. They limited

Jan 1, 1970