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By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1'2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:' Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal'3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.' Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By J. B. Cohen, S. L. Sass

The nucleation process for y', Ni3Ti, is shou'n to change from heterogeneous to uniform as the undercooling within the phase boundary increases. As unifornz nucleation beconres copious, (100) alignment is observed in the early stages of aging; howecer. whether or not the alignment is due to spinodal decomposition could not be determined. The presence oi a large-scale reversible segregation of titanium and not the intermediate precipitate y' may be the cause of the initial strengthening in this alloy system and the discrete regions detected magnetically by Ben-Israel and Fine. Evidence is presented for the role of dislocations in the formation at long aging tines oJ the equilibrium precipitate . ThE nickel-rich portion of the Ni-Ti phase diagram consists of a terminal fcc solid solution of titanium in nickel called y.' For temperatures below 1290°C if the solubility limit is exceeded and the temperature is high enough, the excess titanium will combine with nickel to form q, Ni3Ti, a four-layer hcp ordered structure with stacking sequence ABAC."~ Since a change in structure is involved, formation of q is slow and a metastable precipitate referred to as y' forms. This metastable precipitate is an ordered cubic phase in the unconstrained state having a structure similar to Cu3Au (LIZ) with the composition Ni,Ti."'5 From X-ray studies,8, 7 the following sequence is indicated for the precipitation reaction at low temperatures: 1) The appearance of satellites around low-index diffraction spots and splitting of high-index spots, indicating the formation of a slightly tetragonal phase in an imperfectly periodic arrangement. The tetragonal phase is y' or the depleted matrix, depending on the volume fractions of matrix and precipitate (and hence, the alloy composition); tetragonality apparently arises from coherency strains. 2) The appearance of diffraction spots from the equilibrium second phase, q. Ben-Israel and Fine'" used magnetic methods to measure the changes in matrix composition during aging, and to estimate the precipitate composition in a Ni-10.1 at. pct Ti alloy. They observed that the alloy, solution-treated at 1270°C and quenched, contained heterogeneities with discrete compositions which gradually vanished upon aging. It was suggested that y' may initially form as a defect structure with several possible compositions deficient in titanium as compared to Ni3Ti; the composition Ni3Ti develops with prolonged aging. The initial composition was Ni6Ti which would require a very large deviation in stoichiometry for y'. It was noted that at 700°C the precipitation reaction was 80 pct complete after 2 hr and that the volume fraction of second phase was 0.2 after 1 hr. Mihalisin and Decker' suggested that the equilibrium precipitate, besides being nucleated at grain boundaries, could also form at stacking faults. ~errick" examined the formation of in Ni-Cr-Ti, and suggested that a collapsed vacancy cluster within y' acted as a nucleus for intragranular q at high temperatures, 820" and 900°C. After long aging times at lower temperatures, 650" and 750°C, diffraction patterns taken from regions containing ribbons of stacking faults showed spots associated with q. Aging greatly enhances the mechanical properties of these alloys, even at high temperatures, and the metastable precipitate y' is thought to be responsible.' At 600°C the hardness of a Ni-10.1 at. pct Ti alloy increases rapidly during the first 20 hr of aging and continues to increase slowly thereafter.'" At 700°C the hardness reaches a maximum at 1 to 2 hr and then decreases.l1 In this paper the kinetics of formation of y' and the mechanism of transformation to in a Ni-Ti alloy are described. Evidence is presented that suggests that large-scale regions of titanium segregation are present initially and these may have an important influence on the initial strengthening of the alloy: these regions may be the heterogeneities detected by Ben-Israel and Fine. I) EXPERIMENTAL TECHNIQUES The Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy was prepared by vacuum melting. Its chemical analysis is given in Table I. A 0.007-in.-thick strip was sandwiched between foils of the alloy and placed in an open Vycor tube with titanium chips (to get oxygen) and solution-treated for ; hr at 1150°C in a Globar Furnace under a flowing argon atmosphere. Following a quench into an ice-brine mixture at -5" to -2"C, a sample to be aged at temperatures up to and including 700°C was sealed in an evacuated Vycor capsule before being put into a fused salt bath. Aging above 700°C was carried out on bare samples in a salt bath. When removed from this bath and quenched into an ice-water mixture, the sample was normally coated with a thin layer of oxide easily removed with emery

Jan 1, 1970

By Gerard Matthes

Only in recent years has any practical headway been made in the application of aerial photography to geological problems, and up to the present time its principal value to the geologist and mining engineer has been in "areal geology;" i. e., the study of formations as revealed at the surface. The object of this paper is to set forth briefly the principal advantages that may be derived from aerial photographic data in geological work and to serve in a measure as a guide to those who may be contemplating its use. Geophysical prospecting has for object the locating of mineral under the surface. Inasmuch as the geologist's chief complaint in life is a dual one—inability to see under the surface and inability to visualize comprehensively what he does see on top of the ground—geophysical prospecting coupled with aerial photography should do much to lessen his burdens. To what extent aerial photography can be made a useful adjunct to geophysical prospecting remains to be proved, but the inference drawn here is that it holds many alluring possibilities. To avoid disappointments, it should be stated at the outset that to the geologist or mining engineer an aerial photograph or mosaic is only a tool, the efficient use of which he must set out to master. Upon his skill and ingenuity in applying it to particular problems will depend largely the value of the results that he will obtain. Under the most favorable conditions an aerial mosaic, or even a few loose photographs, because of the exceptionally comprehensive oversight which they afford of field data, such as dips and strike observations at isolated outcrops, local indications of faulting, mineral and fossil finds, greatly facilitate study and correlation, save much tedious foot work, and may repay their cost many times. Even so, types of country may be found where the most skillful use of the best of pictures will produce results so meager as to render the cost of aerial photography entirely unwarranted. Between these two extremes will be found endless variations and possibilities. Hence no set rules can be promulgated. The safest procedure is to treat each case as a separate problem and to carefully weigh the relative advantages and shortcomings of aerial photography before embarking on its use.

Jan 1, 1928

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute's influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger's argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.' Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute's influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute's influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968

By T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,' sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.' The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By S. Kobayashi, A. E. Armenákas, C. Mylonas

Earlier work1-4 has shown that commercial mild steels under static loading at the lowest natural operating temperatures fracture in a brittle manner only when damaged by a suitable history of straining. Notched and then compressed plates have fractured in subsequent tension at loads as low as 10 pct of the limit load and precompressed smooth bars at a subsequent extensional strain as low as 0.01. The comparison of the average net fracture stress with the flow limit stress was shown to be an excellent criterion of brittle or ductile behavior of mild steel structures when only loads and general stress levels are known. The present investigation shows that the deformation at fracture is a far more sensitive measure of brittleness than the fracture stress. Both criteria, deformation and stress, are used to determine the amount of uniform precompression of two mild steels, ABS-B and Project E-steel, resulting in brittle fracture under the strong constraint of a subsequently machined severe circumferential groove. The fracture stress equaled or exceeded the theoretical flow limit Ól = 2.680., ('based on the elevated yield stress at each prestrain) up to prestrains of about 0.20 and then fell off to about 1 at prestrains of 0.60. Yet a prestrain of only 0.05 reduced the elongation at the shoulders by a factor of about 4. The total plastic elongation of a region surrounding a sharp notch in prestrained steel deternines whether or not fracture will be initiated in large structures, hence is a direct and realistic measure of the remaining ductility and provides an excellent test of the material's resistance to embrittlement. ALMOST all engineering structures of mild steel which failed in service in a so-called "brittle" manner exhibited appreciable local plastic deformation (more than 1 pct) and a mixture of "cleavage" and "shear" fracture surfaces. Furthermore, the peak local stress in an advancing crack is always high. Such simple criteria as pure cleavage, absence of plasticity, or fracture stress, so useful in other fields, are insufficient to characterize brittleness in engineering structures at ordnary temperatures. The "brittle)' behavior of engineering structures is caused by the limited ductility at cracks or notch regions, as shown by recent work at Brown University summarized and extended in Refs. 1 to 4. It was also shown that the local ductility of mild steel may be catastrophically reduced by a suitable strain and temperature history similar to those which may occur in real structures. Localized yielding begins at the notch roots at low loads but is contained by surrounding elastic regions. The plastic strains are hence small. They increase slowly with the load up to the flow limit or limit load for an ideally plastic material. Unrestricted plastic flow then occurs. At such strains the real material locally st rain-hardens and fractures. With work-hardening materials no flow limit exists, and the transition from low to high plastic strains is gradual but increases more rapidly at loads close to the flow limit of an equivalent perfectly plastic material. When the available ductility is sufficient for reaching the limit load, the behavior is normal or "ductile". With insufficient ductility, fracture will occur at a low load and will be defined as "brittle". Accordingly the sufficiency or not of the ductility at a notch is reflected in the magnitude of the fracture load or average net stress as compared with the limit load or flow limit. The application of this criterion gave surprising results. Service failures under semistatic loading occurred mostly below the limit load, hence were "brittle". On the contrary all static tests with undamaged commercial mild steels reached the limit load in spite of the deepest notches and temperatures below Charpy impact transition (say about -30°F or higher). Notched bars showed no brittleness even under fully dynamic axial loading up to 1.5 x107 psi per sec at -23°F and about 2.5 x l06 psi per sec at -ll0°F, but broke in a brittle manner at -200°F and l03 psi per sec.' To propagate a fracture at low load, experimenters had to trigger it by superimposing a strong dynamic impact at a notch cooled by liquid nitrogen as in the Robertson5 or Esso tests.' Once started the cracks would run through warmer regions of smaller stress. Obviously the ductility of the apparently undamaged commercial steels was "sufficient" in the laboratory tests but not in the service fracture, where it must have been reduced by some embrittling procedure of fabrication or service. These conclusions were confirmed by the achievement of low static stress (brittle) fracture initiation in unwelded steel after a local reduction of ductility by simple prestraining. Symmetrically notched plates of undamaged mild steel cooled below the Charpy V-notch transition range were tested in central static tension: Undamaged plates withstood loads of limit intensity, but when subjected to prior in-plane com-pressive prestraining perpendicular to the notch axis and to accelerated aging, the plates fractured completely or partially at very low static loads, as low as one-tenth of the flow limit.2-4 However, damage could not be easily related to the strongly variable prestrain around a sharp notch. To obtain easier strain measurements, it was decided to use axially precom-pressed bars and bent bars. Final testing was done by

Jan 1, 1970

By Edward J. Felten

Binary Cr-A1 alloys containing from 2.5 to 30 wt pct Al and 0.7 wt pct Y were heated in oxygen, air, and nitrogen between 1000" and 1200°C. The reacLivity of the alloys was found to be dependent both on the alloy composition nnd the nature of t he atmosphere. In oxygen, nllojs containing up to 15 to 20 wt pct A1 reacted to produce an external scale of Crz03 and a subscale consisting Predominently of Al203. Alloys contazning 20 to 30 wt pct A1 react in oxygen to produce an A1203 external scale and little m no subscale. The latter alloys were markedly more oxidation resistant than those of low alurninum content. In air, the alloys on which an external Crz03 scale was formed were found to be permeable to nitrogen ns evidenced by the copious amomts of chromium and aluminum nilrides observed ns part of the subscale. The reactizities in nir (or nitrogen) of these alloys increase <m their aluminurn contents increase. However, alloys on which Al,O, us an external scale is formed were nol culnerable to nccelerated attack in air, and no eltldence of nitvide subscnles were observed. For all alloys, yttrium serwed pYimarily to improve oxide adhrence. THE role of chromium in the oxidation resistance of Fe-Cr alloys &apos;-&apos; and that of aluminum in Fe-Cr-A1 al10s&apos; has received considerable attention in recent years. This is understandable since many of these alloys have excellent oxidation resistance due to the formation of either a Cr203 or a-Ala03 film between the metal and the oxidizing atmosphere. Small additions of yttrium or other rare earth metals are effective in preventing spalling of the protective oxide from the metal substrate."" In contrast, little is known regarding the oxidation resistance of Cr-A1 alloys, although some work has been done by Tumarov et a1.&apos; The poor niechanical properties exhibited by Cr-A1 alloys make them undesirable for use as structural components, but their use as coatings cannot be disregarded. The use of chromium-rich aluminide coatings for refractory metal alloys is an example of the potential use of this type of sytem. The purpose of this work is to examine the oxidation behavior of Cr-A1 alloys containing 2.5 to 30 wt pct A1 and 0.7 wt pct Y. The effects of temperature, atmosphere, and thermal cycling have been determined. EXPERIMENTAL PROCEDURE The alloys used in this investigation can be divided into two groups. Those containing 2.5, 5, 7.5, and 10 wt pct A1 and 0.7 wt pct Y were extensively evaluated in the temperature range from 1000" to 1200°C. Alloys containing 15, 20, 25, and 30 wt pct A1 and 0.7 wt pct Y were tested only at 1200°C. All of the alloys were prepared by standard arc-melting techniques in the form of cylinders approximately 4 in. long and 19 in. in diam. Wafers were cut from the cylinders and subsequently subdivided into rectangular coupons. The alloys were brittle and therefore some cracks were found in almost all specimens. The coupons were prepared for oxidation by mechanically polishing through 600 grit Sic paper, and were thoroughly degreased just prior to testing. Two types of oxidation experiments were conducted, namely; cyclic tests in which the specimens were examined and weighed after each 2 hr exposure, and continuous thermal balance tests run in a controlled atmosphere (oxygen, air, or nitrogen) for 20 hr. In the former test the spalled oxide was not included when the specimens were weighed. The physical condition of a specimen was noted visually after each cycle and testing was continued either to failure or until the performance of the specimen was well characterized. Both Micro and Semi-Micro Thermal Balances (Ains-worth) were used in the continuous tests. The oxidized specimens were sectioned and prepared for metal log raphic examination. The specimens were polished through 600 grit Sic paper. After polishing through 6 and l p diamond, a final mechanical polish with Linde B-Alz03 was used. Specimens containing 2.5 pct A1 were etched electrolytically using a 10 pct oxalic acid solution at 4 v for about 2 sec. Selected specimens were examined in the electron microprobe analyzer. Oxide specimens were examined by standard X-ray diffraction techniques. EXPERIMENTAL RESULTS For convenience, the test results have been broken down according to the exposure temperature, and further subdivided according to the type of test and atmosphere employed. Because of the poor quality of the specimens a larger than normal amount of scatter was observed in the measured rate constants. Also, the evaluation of the weight gain data was done on a somewhat arbitrary basis and may not be truly representative. However, the results obtained do show a significant trend in behavior regarding both alloy composition and the nature of the oxidizing atmosphere. I) Oxidation Behavior at 1000°C. A) Continuous Oxidation estsin Oxygen. This series of experiments was run in the Ainsworth Micro-Thermal Balance using pure oxygen at a pressure of 76 mm Hg. Under these conditions all specimens oxidized in accordance with the parabolic rate law over a major portion of the exposure time; the rate constants appear in Table I. The oxide formed externally on all specimens was predominantly Cr,O,, which was generally adherent. In some cases a slight amount of spalling in the form of a fine powder was noted. a-A1203 was observed as a subscale, along with Yz03 in all alloys. Alloys containing up to 7.5 wt pct A1 oxidize more rapidly than the Cr-0.7Y alloy.

Jan 1, 1970

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world&apos;s crude oil is produced as emulsions that must be treated (demulsified) to be marketed.&apos; Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-&apos; they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."&apos; Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By Frederic Carter

THERE have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it had not been known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there had been noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals had been meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20. lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or, flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

Jan 1, 1928

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,&apos; however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500&apos; with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By C. F. Tolman

In February 1913, Prof. L. C. Graton and Dr. Joseph Murdochl presented to the American Institute of Mining Engineers a notable contribution to economic geology under the title The Sulphide Ores of Copper. The value of the work was recognized by mine operators, and Mr. Graton was assisted in his plan to extend his investigations, by the organization of a commission to undertake a "secondary enrichment investigation." In this work he secured the cooperation of the Geophysical Laboratory of the Carnegie Institution of Washington. The report2 on the chemical phascs of the investigation has just been published. Incidental to investigations3 carried on in our laboratory of Economic

Jan 1, 1916

By Axel Hultgren, B. Herrlander

THE original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between At and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880° was free from veining. Bannister and Jones4 considered veining in ferrite to be a manifestation of microscopical and submicroscopical inclusions. Northcott,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berglund. Tritton (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling.

Jan 1, 1946

By Gilbert Soler

Producers of alloy steels recognize the importance of chemical composition in relation to the hot-working properties and the typical surface defects found in their product. Each analysis of steel has its own peculiar characteristics. Under conditions of standard mill practice each analysis is susceptible to certain types of defects. Mill practice must be varied to obtain the best combination of surface and internal quality in the product. Chemical composition influences the cast structure and crystallization characteristics of the ingot. It also determines the rate of heating and cooling, the plastic hot-working range, and the phase structure of the steel at various temperatures. as well as the tendency toward scale formation and decarburization. This paper endeavors to emphasize the manner in which chemical composition affects the various properties of steel, and to indicate the relative importance of these factors in relation to the hot-working properties and surface characteristics of killed steel. The influence of chemical composition may be outlined as follows: I. Effect on the cast structure of steel, including: A. State of deoxidation, and type of inclusions. B. Gas content of steel. C. Freezing point and melting point of steel. D. Crystallization characteristics and segregation. 11. Effect on the hot-working properties and surface characteristics of steel, including: A. Plastic hot-working range. B. Phase structures at hot-working temperatures. C. Rate of heating. D. Cooling characteristics. E. Scale formation. F. Surface decarburization. EFferect of Chemical Composition on Cast Structure of Steel State of Deoxidation and Type of Inclu-sions.—The state of deoxidation is limited by the final chemical analysis desired in the finished product, and is controlled primarily by carbon, manganese, silicon, and aluminum, and to a lesser degree by chromium, titanium, vanadium, or other deoxidizing elements. The degree of deoxidation affects the density of the cast structure and broadly classifies the steel as killed, semikilled, or rimming. This in turn manifests itself in surface characteristics. The manner and extent of deoxidation also controls the amount, type, and distribution of nonmetallic inclusions formed. The equilibrium of manganese, silicon and aluminum with the slags and pouring refractories with which the metal comes in contact is important, especially in regard to inclusions of fire-clay origin. Some surface Seams and hot-working difficulties can be traced to nonmetallic inclusions.

Jan 1, 1941

By A. W. Fahrenwald

The physics and chemistry of the flotation process are not well understood. Many papers dealing with the theory of flotation have been published but most have been narrow in their viewpoint. No theory advanced has done more than explain, more or less satisfactorily, various isolated phenomena. Scientists have done little with the problem, doubtless because they have not seen sufficient of the practical side of the subject to have their interest aroused. Any attempt to explain the mechanism of flotation that considers only contact angles, surface tension, adsorption, the floating of needles, flocculation, or any other single and narrow phase of the question is sure to be disappointing. Flotation is a problem of colloid chemistry and must be studied as such. In a broad general way, flotation is a process involving and operating by virtue of surface reactions. The term "surface reactions" may be open to criticisms. Many chemists give the term "reactions" a definite and restricted meaning and to such the term may connote change in atomic grouping in strict stoichiometric ratios. While Langmuir looks upon adsorption as a reaction, and there is much evidence in support of this view, we may look on adsorption as a physcial process as far as this paper is concerned. The term seems well suited to the work in general. Presumably these reactions are reactions between the same kinds of forces (electrical) and differ only in degree and in the surface manifestations produced. This premise seems logical if we accept the theory that the atoms of dl elements are made up of grains of electricity, having mass and charge, called electrons; and that atoms differ from one another only in the number and arrangement of the electrons about a positive nuclear

Jan 1, 1924

By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard&apos; showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.&apos; Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y&apos; eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y&apos; pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By T. A. Wilson, S. L. Hoyt

The plastic deformation of slender single crystals of zinc has been described in some detail in the paper by Mark, Polanyi and Schmid,&apos; which has become a classic, and also by one of the present authors in a somewhat shorter account. 2 The study of single-crystal zinc is termed classical because zinc single crystals offer, perhaps, the best material yet available for the study of atomic behavior during deformation and the effect known as "strengthening" in metals. A considerable amount of additional work has also been done on single-crystal zinc, but as it is not closely related to the present paper it will not be considered. Throughout all the former work, the mechanism of plastic deformation first described by Mark, Polanyi and Schmid has been assumed to hold. This may be said to offer the strongest confirmation of its correctness. Even so, the picture of the process has never been as completely portrayed as is desirable. The first object of the present paper is to describe work that has been done in this field, and which is even yet being carried on, in the hope that a more complete picture may be obtained. Mathewson and Phillips3 have recently described a new mechanism of the deformation of zinc based on their study of large rectangular crystals. One of their conclusions was that deformation produced twinning with a rotation of some of the basal planes into positions 94" removed from their original position; a position almost the same as that of the prismatic planes before twinning. A second conclusion was that fracture occurred along these basal planes in their new position, and, therefore that fractures previously regarded as prismatic were in reality basal. Such findings are of great significance and they raise a question as to the generality of such behavior. Professor Mathewson&apos;s opinion is that even the slender cylindrical single crystals behave in the same manner as his large rectangular crystals when strained by simple tension.

By D. C. Reynolds

Recent experiments with II-VI compounds have shown that they hazle considerable potential for laser applications over a broad region of the optical spectrum. It may be possible to cover the spectrum continuously from 3200A (ZnS) to the far infrared (CdHg:Te) since HgTe is a semimetal. At this writing laser action has been observed in ZnS, Zn0, CdS, CdSe, CdS:Se, CdTe, and some of the CdHg:Te alloys. Of particular interest are those lasers operating in the zlisible and near ultraciolet regzons of the spectrum where detectors of high sensitivity are available. The lasing transitions in II-VI compounds are bound exciton transitions some of which have been identified in auxiliary experiments. High efficiencies and low thresholds for lasing hare been achieved almost exc1usively in plutelet-type crystals. The greater crystalline quality exhibited by the phtelet-type material is shown to result from the crystal growth habit. Phonon scattering- of conduction electrons to the ground-state exciton is discussed ill relution to Lou thresholds and high efficiencies for lasing- observed in the CdS:Se solid solutions. The first successful semiconductor laser operation was achieved in the III-V compounds. It is possible to choose a material in this group that will operate between approximately 0.65 and 8.5 . There are at least two reasons why one would like to have a laser operating at shorter wavelengths. First, it would be easier to experiment with a laser operating in the visible region of the spectrum, and also more desirable to have high-in tensity visible light sources. Second, the most sensitive photomul-tiplier detectors are available in the visible and near ultraviolet regions of the spectrum. It is known that II-VI compounds are direct-band-gap semiconductors and as such offer the potential of operating at any specified wavelength between 3200 (ZnS) and 7772A (CdTe). Light emission from II-VI compounds has been the subject of numerous investigations for many years. These investigations were all primarily concerned with noncoherent emission. It has been only recently that coherent emission from these compounds has been observed. To date, laser operation has been demonstrated in CdS, CdSe, and the solid solutions of CdS:Se, ZnS, ZnO, and CdTe. These compounds cover an appreciable portion of the optical spectrum from the ultraviolet to the near infrared. In considering laser applications, the use of lasers in communication&apos;s systems offers many desirable features. In any operation of this type one must consider the losses in transmitting the radiation from the source to the detector. Atmospheric absorption in the visible and near ultraviolet is variable and greater than in certain regions of the infrared. It might be concluded that for long-range communication systems an infrared laser operating in a spectral region that is coincident with a transmission window in the atmosphere would be preferable. However, one cannot overlook the possibility of operating a system in the sensitive region of a highly sensitive photomultiplier detector or other light-amplifying system. LASER CONSIDERATIONS To produce a source of coherent radiation it is necessary to achieve a population inversion. In the case of semiconducting materials it is necessary to raise the electrons from one energy state to a higher-energy state relative to it. In semiconductors, this population inversion can be achieved by three different techniques: 1) Current Injection. This technique uses a p-n junction biased in the forward direction. Large numbers of electrons are injected from the n region into the p region, and recombination occurs close to the junction. An inverted population is obtained in this region and the recombination radiation propagates parallel to the junction. This type of pumping has been used in the GaAs junction-type lasers but has not been successfully employed in the II-VI compounds. 2) Optical Pumping. In this case, one uses photons to obtain a population inversion by exciting electrons to higher-energy states. The pump sources are flash lamps or arc lamps and, occasionally, other laser sources when such sources have the appropriate energy for exciting the electrons. The disadvantage of this type of pumping is that flash lamps put out a rather broad spectrum of radiation, whereas the laser material has a rather narrow region of absorption. This results in an inefficient process. Laser sources provide efficient pump sources but the number of usable wavelengths is limited. 3) Electron Beam Pumping. In this technique, the laser sample cavity is bombarded with electrons having energies in the range from approximately 10 to a few hundred kv. The bombarding radiation excites electrons from valence to conduction band states in the semiconductor, giving rise to an inverted population. This type of pumping has been used successfully in several 11-VI compounds.

Jan 1, 1968

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.&apos;-&apos; Komatsu and rant&apos; in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov&apos;s analysis12 of the distribution of spheres of varying size. DeHoff&apos;s analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By Gilbert Soler

Producers of alloy steels recognize the importance of chemical composition in relation to the hot-working properties and the typical surface defects found in their product. Each analysis of steel has its own peculiar characteristics. Under conditions of standard mill practice each analysis is susceptible to certain types of defects. Mill practice must be varied to obtain the best combination of surface and internal quality in the product. Chemical composition influences the cast structure and crystallization characteristics of the ingot. It also determines the rate of heating and cooling, the plastic hot-working range, and the phase structure of the steel at various temperatures. as well as the tendency toward scale formation and decarburization. This paper endeavors to emphasize the manner in which chemical composition affects the various properties of steel, and to indicate the relative importance of these factors in relation to the hot-working properties and surface characteristics of killed steel. The influence of chemical composition may be outlined as follows: I. Effect on the cast structure of steel, including: A. State of deoxidation, and type of inclusions. B. Gas content of steel. C. Freezing point and melting point of steel. D. Crystallization characteristics and segregation. 11. Effect on the hot-working properties and surface characteristics of steel, including: A. Plastic hot-working range. B. Phase structures at hot-working temperatures. C. Rate of heating. D. Cooling characteristics. E. Scale formation. F. Surface decarburization. EFferect of Chemical Composition on Cast Structure of Steel State of Deoxidation and Type of Inclu-sions.—The state of deoxidation is limited by the final chemical analysis desired in the finished product, and is controlled primarily by carbon, manganese, silicon, and aluminum, and to a lesser degree by chromium, titanium, vanadium, or other deoxidizing elements. The degree of deoxidation affects the density of the cast structure and broadly classifies the steel as killed, semikilled, or rimming. This in turn manifests itself in surface characteristics. The manner and extent of deoxidation also controls the amount, type, and distribution of nonmetallic inclusions formed. The equilibrium of manganese, silicon and aluminum with the slags and pouring refractories with which the metal comes in contact is important, especially in regard to inclusions of fire-clay origin. Some surface Seams and hot-working difficulties can be traced to nonmetallic inclusions.

Jan 1, 1941