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By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By John J. Egan, W. D. Forging, Walter Crafts

Although many elements reduce the tendency to porosity in steel castings, manganese, silicon, aluminum, calcium, titanium and zirconium appear to be most generally suitable for the purpose. The manganese and silicon contents are usually maintained in a fairly constant range. Silicon-killed castings often are made to be sound with little or no addition of the stronger degasifiers. In many cases, however, it is more practical to utilize the stronger degasifying elements, aluminum, calcium, titanium and zirconium. Since they greatly modify the composition, shape, and distribution of the nonmetallic inclusions, and thereby the ductility, the strong deoxidizers must be used in such a way as to form the least harmful types of inclusions. As the reasons for failure always to obtain good results have not been obvious, an effort has been made to determine the mechanism of solidification of steels deoxidized to produce certain types of inclusions. Diagrams representsing the mechanism of their formation have been constructed from the appearance of the nonmetallic constituents and have not only illustrated the limiting features of specific deoxidizing treatments with respect to inclusion formation and ductility, but have also indicated a relation between inclusions and resistance to hot tearing. Three different types of deoxidation treatment have been used for obtaining sound castings with relatively high ductility. The first method is to make and cast the steel under such conditions that deoxidation with silicon and a small addition of a strong deoxidizer assures soundness. The effective addition that will promote soundness without causing the formation of intergranular inclusions varies with the furnace practice and composition, but may be limitled to about 0.025 per cent Al, Zr or Ti. Up to 8.10 per cent Ca and 0.15 per cent V are also used for this purpose. The inclusions in these steels are characteristically glassy silicates and round or irregular sulphides. As pointed out by Sims and Lillieqvist,1 the formation of fine intergranular inclusions, which are detrimental to ductility, limits the amount of strong deoxidizers that may be added.

Jan 1, 1940

By M. E. True, B. L. Stone

To cope with the problems encountered when drilling at greater depths and to reduce the amount of physical effort required on the part of drilling crews in making round trips, a new type of semiautomatic power-operated drilling machinery has been developed which permits round trips to be made without the drill pipe being touched by hand. This equipment consists of hy-draulically operated tongs which perform the stabbing, spinning, and tong-ing operations, and two power-operated racking units mounted in the derrick for carrying the pipe to and from the center of the hole and positioning it on the mat and in the rack. With this equipment all of the operations of the various units are controlled remotely by manipulation of hydraulic valve levers and electric switches. INTRODUCTION As horsepower rises to meet the demand for deeper drilling, it is necessary to increase the weight of surface drilling equipment. Also, the duration of repetitive operations in making round trips to change bits is greatly increased with depth. Harder formations encountered at greater depths reduce bit life rapidly, resulting in more frequent round trips and in some instances more time is consumed in changing bits than in drilling. Since the introduction of the first rotary employed to drill for oil in 18951, there has been relatively little change in the general procedure for making up, breaking out, stabbing, and racking drill pipe in making round trips to change bits. The conventional method of making round trips with the drill pipe requires that drilling crews lend strenuous physical assistance to manually operated tools. Although many new devices have been developed to improve efficiency, increase speed of making round trips, improve safety, and reduce the amount of physical effort required in handling drill pipe, it is considered a vital necessity to substitute automatic or semiautomatic power-operated machinery for many of our more or less manual operations if extremely deep drilling is to be carried out successfully on a production basis in the same manner as our shallower drilling of today. Field tests have been made of remotely controlled power-operated tongs, spinner, stabber, and racking equipment. The tongs, which include a built-in pipe spinner, are mounted on a column, are capable of gripping and supporting the weight of a 90-foot stand of drill pipe, and are provided with means for moving the pipe vertically as well as to and from the center of the hole. The racking equipment consists of two units, one at the level of the conventional monkey board and the other at the first girth on the ladder side of the derrick. Most of the physical effort of making round trips with drill pipe has been eliminated in that all of the operations of tonging, spinning, stabbing, and racking of pipe on the floor are controlled by an operator in a seated position by manipulation of hydraulic and electric valve levers and buttons. The driller is relieved of operating the cathead, leaving only the hoisting and slips to be controlled. Complete round trips are made without the drill pipe being touched by the drilling crews. Although the speed of pulling or running a single stand with the power-operated equipment is approximately the same as that with conventional equipment, it is possible to maintain this rate for long periods, whereas fatigue slows crews working conventionally during round trips, especially under adverse weather. After completing round trips with this equipment, drilling crews are not exhausted, consequently, are able to perform effectively their duties while drilling, which is essential for maximum over-all efficiency. Safety is substantially improved as the derrickman performs his duties from a platform enclosed by rails and the tong lines and spinning chain are eliminated from the derrick floor. The hazards encountered in racking drill pipe on the floor and in stabbing are also eliminated. Figure 1 shows a drawing of a derrick equipped with the power-operated drill'pipe handling equipment.

Jan 1, 1949

By B. Ramaswami, Y. Nakada, U. F. Kocks

Compression tests were performed on single crystals of aluminum, silver, gold, and a Ag-10 pet Au alloy, with height-to-width ratios from 8:1 to 1:1. As this ratio decreased, so did the amount of easy glide until, for cubic specimens of all the pure materials, it was entirely absent. Heterogeneity of deformation is proposed to he a major contribution to the explanation of easy glide in slender specimens. For comparison, one single-crystal cube of zinc was tested and showed a behavior very similar to that in tension. Beyond easy glide, tension and compression curves are very similar. It is concluded that, in this range, neither grip effects nor orientation change influence the work-hardening characteristics to any significant extent. (121) and (100) crystals of all materials had similar stress-strain curves in tension and compression, except that the stress level of the flat portion of aluminum (109 crystals at high strains mas somewhat higher in compression. These results are at variance with previously proposed mechanisms of orientation dependence by both Hosford and Kocks. The compression tests themselves are described in detail and it is shown that they are essentially frictionless and produce single slip when the crystal is suitably oriented. DEFORMATION in uniaxial compression does not necessarily give the same result as deformation in uniaxial tension, essentially because the boundary conditions chosen are practically always different. 1) The shape and size of the specimens are usually different, and any genuine effect of size on work hardening should thus influence the result. 2) The grip constraints are usually different and can vary substantially for different kinds of tests. If the compression specimen is a thin plate and the friction on the platen is large, the grip contraints are more serious than in tension and lead, in the extreme, to uniaxial strain rather than uniaxial stress. If the specimen is roughly cubical and the friction is low, the specimen is less constrained than in tension inasmuch as displacements in the contact face are allowed. 3) The orientation change of single crystals is of opposite sign in tension and in compression; it is furthermore different in detail, because the relevant orientation in a squat specimen is the normal to the contact face, whereas that in a slender specimen is the generator of the side faces.' The considerable dependence of work hardening on the initial orientation in tension would suggest that the orientation change should also be very important. 4) Finally, localized deformation instabilities found in tension tests, such as necking and Lüders band propagation, are not possible in squat specimens. This is, for some investigations, a favorable consequence of the large grip influence. Even if one is not interested in any of the effects mentioned above, compression tests are often desirable just because the specimens needed are so much smaller and sturdier. For example, they have been very helpful in the investigation of latent hardening by means of alternate longitudinal and lateral compression of cubes,* and for testing

Jan 1, 1964

By Albert Stazicker

AT Climax the warehouse department operates as an independent unit similar to the mine and mill departments. It has the responsibility of receiving, checking, unloading, and storing all material and supplies delivered to the plant. In addition, the transportation of all supplies comes under the direction of the warehouse so that prompt delivery of supplies to all departments is one of its major functions. The transportation division operates heavy and light trucks, trailers, two large tractors, and two snowplows. In addition to delivering supplies it is also responsible for snow removal from the roads, hauling of sand and gravel for concrete and domestic coal to employees. and all miscellaneous work involving the use of tractors or trucks.

Jan 1, 1946

By S. G. Lasky

EVENTS during and since the war indicate that the nations of the world are trying to initiate an era of international co-operation. Definitions and objectives include social, economic, and human considerations no less than political considerations. The mineral resources of the world and the absolute and relative position of each nation enter into this situation. The possible use of armed might, the application of sanctions, the international flow of commerce, the ways in which this flow may encourage or hamper international well-being, and the influence of international and domestic well-being upon one another are all matters that must take mineral resources into account. If the United States is to act wisely and forthrightly in such matters we must be thoroughly informed as to our position with respect to mineral resources. What is the mineral position of the United States? A variety of widely conflicting opinions are held in authoritative and intelligent quarters: (1) For practical purposes our mineral resources are already exhausted.

Jan 1, 1946

By HAROLD A. KNIGHT

The Miami Copper Co., Arizona, is asking Congress to reimpose the import duty of two cents per pound on copper which, by law, has been suspended until June 30, 1950. C. Donald Dallas, chairman of Revere Copper and Brass, champion of a duty-free regime as regards the red metal, has been answering E. H. Westlake, Miami president, now that Mr. Westlake's statement to stock- holders has been salted away for posterity on wire recorders. Even prior to this action and at the instigation of two prominent consumers of pig lead, the House of Representatives has, in the confines of committee, not yet reported out, as of June 16, a bill to suspend the duty on lead for another year from expiration of the present law June 30, 1949. But apparently the bill was started too late. Thus the tariff issue becomes a Rip Van Winkle again after having slept for several years in the mountains of metals scarcity. During the wartime scarcity and the boom days that followed, most metal producers welcomed a considerable influx of foreign metal since it gave them a little surcease from constant teleibhone calls asking why that delivery of 300 tons of lead, 250 tons of zinc, and 1000 tons of copper had been delayed. These were the days when it was such an undisputed sellers' market that the sellers had even thrown away their certificates of ownership. Another development that brings home the tariff situation, small in it- self but perhaps indicating a trend, has been the announced closing of

Jan 1, 1949

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By R. B. Schluter, M. M. Fine

Processes for manufacturing prereduced pellets have heretofore required temperatures of 2100°F or higher. Sulfides will accelerate the liquid-phase sintering of metallic iron, yet do not deter the reduction of iron oxides. The sulfides may be introduced as gases to the kiln atmosphere or as solids in the re-ductants. The net result is that well metallized iron pellets with good crushing strength can now be produced at a little over 1800°F. One of the most persistent topics at technical gatherings and in the recent scientific press has been the reduction of iron ore. In May 1960, a symposium on the subject was sponsored by the Electrochemical Society. The proceedings, comprising two dozen papers, were later published.' More recently, in November 1966, a similar gathering took place at Michigan Technological University, Houghton, Mich. The latest meeting was the International Congress on Production and Utilization of Reduced Materials at Evian, France, in May 1967. If the volume of literature, symposia and conferences is a measure of industry concern, then the current interest in reduction must be at a high level. Barrett,2 one of the early pioneers, stated some years ago that "The history of sponge iron has been so discouraging that many men in the iron and steel industry are violently opposed to giving it any further consideration." In spite of the "violent opposition" noted by Barrett, research people in and out of the industry continue to be attracted by the elusive prospect of uncovering a simple, viable means of direct reduction. Wild,3 one of the speakers at Evian, listed no less than 48 direct reduction processes (laboratory, pilot plant and commercial). Some of these were of historical interest only, but many others had resulted from developments within this decade. The previous big thrust into direct reduction occurred under the artificial impetus of a wartime economy (World War 11) and was largely an effort to provide more melting stock without coke ovens and blast furnaces. The present-day inquiry is proceeding at a more leisurely pace and the emphasis is different. For one thing, there is much less anxiety to circumvent the blast furnace. On the contrary, a whole new research endeavor has grown from the discovery that metallized burdens are exceptionally productive.4 Although the search for a melting stock

Jan 1, 1970

By D. O. Hobson, P. L. Rittenhouse

We have recently found that many lots of Zircaloy-2 and -4 tubing tested in tension deform to cross section shapes that are "polyhedral" rather than circular. The noncircular cross sections seem to result from a circumferential variation in plastic proper -ties and, therefore, in texture. We examined the diffracted X-ray intensity from (OOOl), {1010), {ll20}, and {1011} planes parallel to the tubing surface around the entire circumference. Tubing that deformed to a circular cross section showed <5 pct variation in diffraction intensity around the circumference from any of these planes. Greater intensity variations were found for all the tubing materials that developed non-circular cross sections during deformation. In each instance the number of intensity maxima and minima was consistent with the number of sides of the &apos;polyhedral" cross section. THE effects of crystallographic texture on the mechanical properties of zirconium, zirconium alloys, and other anisotropic hexagonal materials such as titanium and hafnium have been intensively studied. If the natural crystallographic anisotropy of these materials could be controlled by selected fabrication operations, a material could be produced with a texture, or preferred orientation, in which the maximum strength directions are in the stress directions of the structure. The permissible stress levels of the structure could then be increased. Rittenhouse and Pickle-simerl have shown that highly textured Zircaloy-2 plate can vary from 52,000 to 70,000 psi in tensile yield and from 62,700 to 122,000 psi in compressive yield strengths as a function of specimen orientation. Similar texture effects have been observed in Zircaloy tubing, whose mechanical properties differ depending upon whether the tubing has basal poles predominantly radial or tangential and upon the mode of testing. These same texture effects might be troublesome if the texture in the tubing is not uniform around the tube walls. This paper is concerned with the effects of nonuniform texture on the strain behavior of commercial Zircaloy tubing. BACKGROUND Previously, various lots of commercial Zircaloy tubing were tested under selected stress conditions as part of a program to determine the four quadrants of the yield locus. One of the testing procedures was uniaxial tension and it is the influence of texture variations on the tensile deformation behavior of the tubing that is of interest here. The effect of texture on the strain behavior in tubing is very apparent from a uni-axial tensile test.2 This behavior is illustrated schematically in Fig. 1 for three different tubing textures: 1) basal poles predominantly in the radial direction; 2) basal poles predominantly in the tangential direction, and 3) basal poles equally distributed between the radial and tangential directions. In the first example most of the grains are oriented for prism slip to operate to allow axial lengthening and diametral reduction of the tube. Reduction in wall thickness requires {1122} twinning, a more difficult operation than slip.* In the second example, the texture is such that *The singleCrystal analogy will be used quite often in this paper when strong texturesare being discussed. The textured material is assumed to react as if it were a single crystal aligned in the same orientation and under the same stress system as the predominant texture._____________________________________________ prism slip operates to give axial lengthening and wall thinning. Diametral reduction requires twinning and again should be more difficult to accomplish. A specimen with basal poles equally distributed between the radial and tangential directions should exhibit about equal diametral and wall strains.* Table I shows the *Diametral strain is accomplished by a combination of circumferential and longitudinal strains. But, for the purposes of this paper, it will be considered as a strain causing a change in the length of a specified diameter.__________ strain behavior of two lots of tubing with different textures. The first tube has a texture with basal poles equally distributed between the radial and the tangential directions. The ratio of true thickness strain to true diametral strain is almost unity. The second tube has a predominantly radial basal pole texture and it is apparent that most of the total strain has occurred by diameter reduction, just as one would predict. There is over three times as much diametral strain as thickness strain. RESULTS We found that specimens from certain lots of commercially fabricated tubing did not retain round cross sections during uniaxial testing. Instead, the speci-

Jan 1, 1970

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel&apos;&apos; and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel&apos;s and Arafa&apos;s studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969

By U. N. Bhrany, J. H. Brown

The specifications of particle size and the size analyses of fine particulate materials are commonly presented without reference to the method of analysis. A review of the various sizing methods showed that not only numerous sources of error but also different definitions of size are inherent in the different methods of analysis. To demonstrate the magnitude of the differences, the size distribution of finely crushed quartz was determined by several methods and a critical comparison of the data was made. The experimental results show that appreciably different sizes may be indicated for one material depending on the method of analysis used. However, because the shape of the size-distribution curves determined by almost all methods was constant, a simple method of correlating the data can be adopted. Conversion factors, by which size measurements obtained by the various methods can be expressed in terms of screen sizes, are presented as one method of correlating the results. The size analysis and size specification for lump rock and particulate materials are commonly determined with sieves. With this technique, a readily reproducible measure of size can be obtained merely by duplicating the sieve and the method of sizing. For coarse materials, such as lumps of rock, this technique is simple and effective; and the effects of properties of the material such as shape can be readily understood. When very small particles are measured, however, problems arise. Small sieves are difficult to construct and maintain, and size separations become sensitive to the analytical procedure. For these difficult sieve sizes and for still smaller particles, other sizing techniques employing, for example, sedimentation, light extinction, and microscopy are available. Because these various techniques employ different size-dependent responses to establish size, it is appropriate to examine them and the results they yield to determine their relationships and their limitations. The &apos;size&apos; of a lump of rock is not an absolute quantity, but rather a defined one. With sieves, for example, the size is defined by the screen aperture and no reference is made to the actual shape of the particle, yet only in the case of a regular body, such as a sphere, can the sieve size be related to the shape. With sieves only two dimensions of a particle can be suggested, for the sieve makes no allowance for the length of the particle passing through an aperture. Similarly, the size of a particle as measured by a microscopic technique need bear no relationship to the size as measured by sieves, although the two measurements may be related statistically. In fact, all size measurements are not only defined quantities, but the measurement actually used is an average that is controlled by the technique employed and, hopefully, reflects the property in question of the material of interest. Many papers have been presented that illustrate the accuracy of the various sizing methods, present the advantages of certain methods for certain applications, and describe the principles and technical backgrounds of the various methods. No attempt will be made in the present paper to review this work in detail. The purpose of the present paper is to examine the limitations of the various sizing methods, and to demonstrate experimentally the relationships between the sizes as determined by the various methods of analysis. It is hoped that by recognition of these limitations and relationships, errors in size specification and size interpretation will be avoided. REVIEW OF SIZING METHODS In specifying the size of a material, not only the data but also the method of measurement must be stated. For example, the size of the lump might be specified as its total volume, as its weight, as its maximum dimension, or as its minimum cross section; any one definition might be completely satisfactory for one problem, but not for another. In practice, size analyses follow four basic approaches and fortunately, the conditions that restrict each approach are known. These major methods include: 1) screen analysis, 2) direct measurement of particle dimensions, 3) determination of equivalent spherical size in response to fluid flow, and 4) specific surface determination. Each of these techniques has several variations and some new techniques are also available, but the limitations of the basic techniques are sufficient to permit at least a preliminary

Jan 1, 1962

Jan 1, 1936

Jan 1, 1936

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Jan 1, 1947

Jan 1, 1919

By K. J. Anusavice, R. T. DeHoff, A. G. Guy, T. B. Lindemer

As one oi the approacizes to understanding multicorn-ponent dimsion, an expevinzental sturly is being jnade of tracer diffusion in the copper corner of the CLI-Ni-Zn syste?n, out to 30 at. pct each of nickel and zinc, and in the 150°C range oJ temperature just below tlze solidts te?rlperature. The reslts obtained using the Znm isotope are reported heve, while studies with nickel and copper isotopes are planned for a future paper. The fifteen alloys investigated were melted in sealed wear lubes, sroaged, homogenized, and then analyzed, using the conventional isotope-plating plus lathe- sectiorzing teclzniqlte. The data obtaiued show that the difJusion coeflcient of the zinc isotope increases titlz increase in zinc content, and decreases t&apos;itlz incease in nickel content. The correlation xith solidus temperature is particularly strong. Diffirsiui-ties ranged fro u sq cm per sec nt tlze Iiigh-zinc, low-nickel compositions. The activation energy /or tracer diffusion ravied j.or 31.000 to 54,000 calper mole. It is now generally recognized that diffusion data and theories are needed for multicomponent systems, where extensive practical developments and even some theoretical studies have already been made. For example, much recent work on precipitation from solid solution has been concerned with ternary solid solutions such as A-M-Z&apos; while Zener relaxation has been studied on Au-Ag-Zn alloys,&apos; although adequate diffusion data are available for neither of these systems. Actually, the only ternary systems for which systematic diffusion studies have been begun, in addi- tion to the one reported here, are CO-i-cr3 and Cu-A-Au. Since the theory of multicomponent diffusion is still in the stage of active development5 it is important to distinguish the various kinds of diffusion data that can be determined. An oversimplified approach, widely used prior to 1950, was to determine the influence of a third element, such as nickel, on the diffusion behavior of a binary alloy, such as CU-Z. Later it was recognized7 that four diffusion coefficients can be used to describe ordinary interdiffusion in a ternary system, while as many as six coefficients may be required to include the Kirkendall effect. It is likely that the number of independent coefficients will be shown to be less than four and six, respectively, through the application of the thermodynamics of irreversible processes.5 The simplest type of diffusion in a multicomponent system is tracer diffusion, since each component is characterized by its own tracer-diffusion coefficient in an alloy of a given composition. Thus, in a ternary alloy there are three tracer-diffusion coefficients, each a function of composition and temperature. The present research program is a study of tracer diffusion in the copper corner of the Cu-Ni-Zn system out to 30 at. pct each of Ni and Zn in a 150°C range of temperature just below the solidus temperature. The

Jan 1, 1967

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto&apos; proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer&apos;s analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956