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By Earle C. Smith

The Chairman.—Mr. Earle Smith has kindly offered to make some remarks in connection with segregation in the product, Mr. Smith: E. C. Smith,* Cleveland, Ohio—I will start this Off by a story oF the code days of the American Iron and Steel Institute. In those days, Republic did not have a big strip mill, and the question came up of the check analysis of rimmed steel. I suggested that they let me be the chairman of the Committee on Accumulating the Information on the Variation of the Composition of the Ingots of Rimmed Steel. Somebody wanted to know why I wanted to be the chairman. I said, "we don't make any of the big ingots of rimmed steel, and no matter who makes them they are so bad that you don't dare publish the information. So if 1 collect it and hide it you can't charge me with having done anything that really disrupted the commercial situation." So, everybody furnished me with a rather complete story as to the horrible variations in big rimmed ingots. I took it out to my house and put it away, and it is still there. Now, segregation in the big ingot is no longer an "academic " matter as far as I am concerned. I am in a situation like that of the German who was told in 1956 about the coming war. He said: "until it is your throat that is going to be cut, you don't pay any attention to what is happening to the otherman." 'That is the way with the problem that we have in front of us. Recently I have been told that the 'Omptroller was questioning the payment for certain articles of stamped steel that had been made from rimmed steel, because upon check analysis of the rimmed steel it had been determined that these stamped articles were nut within the compositions that were included in the specification, and therefore he as the camptroller had no alternative. It was not meeting the specification; therefore, no payment. So I I say to all of you: You can very seriously consider this matter of segregation now and on into the future on the basis of the fact that it is actually going to cost your companies, which are making these products, money unless there is some new idea about the infallibility of quantitative , chemists who analyze some of these products or lawyers who read specifications, I don't know which man is going to be the major factor in the future. if the National Bureau of Standards could in some way show the specification writers the variation between good chemists analyzing for That they expect to be umpire eel. the writers would certainly realize that some of the to to which we have calmly signed our names as being O.K. are— well, as one man said to me, they might be filled by the devil, and they certainly could be filled by the Lord, but they could not he me by mankind. I would like to inject two or three things into a segregation study which I Want you to think about, because 1 would be a little surprised if there is very much discussion of them, In the first place, we generslly make steel in the United States in the basic open hearth, and I do not think there has bee,, nearly enough consideration given to segregation German the bath before it moves into the ladle. I am sure that any of the people who handled the 9400 series of the NE series when it contained the 0,60 per cent silicon have more respect than they had previously for the segregation that is within, the ladle; that is, before the metal reaches the ingot mold, the frozen ingots and the segregation in them. Another pint to which I think We ought to sis serious consideration is the segregation of iron oxide in the ingot-iron type of material, where the distinction between that and the steel segregation is that it is actually segregat. ing iron oxide, Normally we are segregating some form of carbon or sulphur, or something like that, with the stamping steel industry now coming down into the ranges of chemistry, where the segregation of iron oxide will be just

Jan 1, 1945

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r') Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r') phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y') phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7') phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y') phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y') phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH'S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.' The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.'-'2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;' 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;'" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4'= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12'13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,')' while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont's TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The a-p type alloys are subject to a loss of tensile ductility with increasing hydrogen content. No hydride phase is visible in embrittled a-B type alloys. The embrittlement encountered appeared to be of the strain-aging type. Both compositional and structural factors are shown to influence the hydrogen tolerance of a-B type alloys. IN previous papers by the authors, the effects of hydrogen on the structure and mechanical properties of high-purity and commercial-purity titanium were described. It was shown that the presence of hydrogen in these materials results in a hydride phase having low solubility at room temperature. This insoluble phase had little effect on the room temperature tensile properties, but did decrease the notch-bar toughness to a large degree. The binary Ti-H systemz indicates that hydrogen is much more soluble in £ than in a-titanium. Hence, it is not expected that the embrittling effects of hydrogen in a-fi alloys will be similar to that found in a alloys. Materials of this type studied in the present investigation included two commercial a-/3 alloys, Ti-8Mn and Ti-4A1-4Mn; three high-purity Ti-Mn alloys containing 3, 6, and 9 pct Mn; and four high-purity Ti-Mo alloys, Ti-SMo, Ti-10.9M0, Ti-13.1 M0, and Ti-20M0, of the a-B and B types. Materials and Fabrication—The high-purity base alloys, composed of iodide titanium and high-purity metals, were prepared by double arc melting under argon in a water-cooled copper crucible, using a water-cooled tungsten electrode. Radiographic examination showed homogeneous Ti-Mo alloys. The analyses of the alloys used in this investigation and their as-fabricated hydrogen content, where determined, are listed in Table I. The two commercial alloys were 1/2 and % in. diam bar stock. No analyses other than hydrogen content were made. In order to maintain the a-B relationship existing in the two commercial alloys, vacuum annealing and hydrogenation were carried out in the B field prior to final fabrication. Fabrication then was done by The three high-purity Ti-Mn alloys were forged to 3/4 in. diam rods at 1600°F, and hot swaged to 1/2 in. diam at 1380°F. Machined and degreased bar stock was vacuum annealed or hydrogenated, fabricated to 1/8 in. diam rod by hot swaging, annealed in argon for 1 hr at 1380°F !75O°C), and water quenched. The six yz lb Ti-Mo ingots were forged to Wi in. diam rods at 1600°F and then hot swaged to % in. diam. Machined and degreased specimens were vacuum annealed or hydrogenated in the /3 field, prior to fabrication, by swaging to Y4 in. rod at 1400°F. After fabrication, the 5 and 10.9 pct Mo alloys were annealed in argon for 16 hr at 1290°F and water quenched to give equiaxed a-B structures. The higher molybdenum content alloys were argon annealed 4 hr at 1470°F and water quenched to give all £ structures.

Jan 1, 1957

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

By L. Himmel, R. F. Mehl, C. E. Birchenall

The rates of self-diffusion of iron in artifically prepared wustites of various compositions have been determined using the decrease in surface activity technique. Similar measurements are reported for artificial magnetites of nearly stoichiometric composition and for natural hematite single crystals. These data, together with appropriate thermodynamic data derived from the present study or from the literature, are used to calculate the rates of oxidation of iron and its oxides, taking as a basis the theoretical rate equations developed by Wagner. The calculations are compared with experimental rate constant data for these same reactions and are shown to provide essential confirmation for the Wagner theory. For the most part, the results are also consistent with the previously proposed transport mechanisms in the oxides of iron. WHEN a metal is exposed to an oxidizing atmosphere at elevated temperatures, a superficial oxide layer is formed which then thickens according to some characteristic rate law. Provided that the oxide layer is dense and continuous and does not present any paths for gaseous diffusion, continued growth must inevitably involve the migration of the reactants—either the metal or oxygen or both—through the lattice of the solid oxide. This is true whether the reaction rate is controlled by the diffusion process itself or by a slow step in a reaction at one of the interfaces. If the overall rate is limited by diffusion, and if the concentrations or thermodynamic activities of the reactants at the boundaries of the oxide layer are independent of time, the familiar parabolic rate law is observed. Under these conditions, Wagner1 has shown that the rate constant may be expressed in terms of the mobilities of the reacting components and the appropriate concentration or activity gradients which are established across the growing oxide layer. In presenting the phenomenological basis for the theory, Wagner has emphasized the role played by lattice defects in diffusion processes in oxides. The essential validity of this theory has been confirmed by experiment for a number of simple systems including the growth of Cu2O on copper.'-' One of the objectives of the present study has been to extend the Wagner approach to the more complex process of the oxidation of iron and its oxides, and particularly to wustite, which is normally the major constituent of the oxide scales formed on iron at temperatures above approximately 570°C. For this purpose the rates of self-diffusion of iron in w?stite, magnetite, and hematite have been measured by tracer techniques and the necessary thermodynamic data have been obtained from equilibrium studies involving the oxides and their atmospheres. These data have subsequently been used to test the underlying assumptions of the Wagner theory as well as the detailed mechanism of the scaling of iron previously proposed by Davies, Simnad, and Birchenall.5 Lengthy treatments of diffusion and conduction phenomena in ionic crystals have been published." * The latest, by Jost,8 also summarizes much of the existing experimental data. In general, however, the oxides of iron have not been considered specifically and hence a brief review of the available

Jan 1, 1954

By Walter B. Lenhart

Introduction and Importance of the Industry Sand, as described in this chapter, is a crude product used for ballast on railroads and highways, and as the fine aggregate in concrete, mortar, plaster and in asphalt paving materials. The sand used in glass, as a molding sand, and as a source of silica is described in Chapter 43. Sand and gravel together constitute the mineral raw materials of largest volume produced from the earth. In 1958, as reported by the U.S. Bureau of Mines,21 680,080,000 tons of sand and gravel (including industrial sand) were produced in the United States. The nearest competitor was crushed rock of which 532,818,000 tons were produced. Coal, both bituminous and anthracite accounted for only 431,616,689 tons in the same year. In dollar value, sand and gravel were exceeded only by cement, crushed rock and fuels. Hence it is a major unit of the mineral-producing industry. As an example, one plant in California operates around the clock at an average rate of 1,500 tons per hour, and at peak intervals has shipped over 4,000 tons per hour, all by trucks. Nevertheless, it is controlled by one man through a panel of push buttons that control the crushing, screening, washing, grading, stock piling, and reclaiming of the products. Because sand and gravel are low-valued commodities, but are used in every construction undertaking in every city, village, farm, dam and highway, they are produced in almost every county in the United States and southern Canada, by thousands of individual operators, very few of whom operate in more than one community. Many operations, particularly those established to supply the needs of major dams that are under construction, or of major segments of new highways, are temporary in nature, and the equipment installed is more or less portable. Because of the bulky nature of sand and gravel, there is very little interstate movement, and almost no exports or imports, except a little movement back and forth across the border of the United States and Canada. First, the material needs definition. Definitions Sand and gravel have been defined as continuously graded unconsolidated materials that appear in the earth's surface as a result of the natural disintegration of rocks. Both normally appear together, but in a wide variety of sizes, types and range of size classification. The American Society for Testing Materials has tentatively revised its definition of "sand" as: granular material passing the 3/8-in. sieve and almost entirely passing the No. 4 (4760-micron) sieve and predominantly retained on the No. 200 (74-micron) sieve, and resulting from natural disintegration and abrasion of rock or processing of completely friable sandstone (ASTM Designation C 58-55T). The Society's tentative revision of its definition of "gravel" is: granular material predominantly retained on the No. 4 (4760-micron) sieve and resulting from natural disintegration and abrasion of rock or processing of weakly bound conglomerate (ASTM 125-55T). Sand and gravel deposits contain materials from the finest silt to the largest boulders. Chemical definition of the two materials is nearly impossible. Sand and gravel always are

Jan 1, 1960

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

By Herbert J. French

Herbert 1. French (Member 1934), vice president of the International Nickel Co. Inc., assistant vice president of the International Nickel Co. of Canada Ltd., and AIME Howe Memorial Lecturer for 1956, died in Rochester, Minn. on Aug. 17, 1955, after a long illness. Before his death, Mr. French had laid the foundation of research on which the Howe Memorial Lecture (p. 770) was based. His associates at Inco, 0. 0. Miller and J. W. Sands, were able to complete the project, present the lecture, and prepare it for publication, following Mr. French's general outline. Born in New York on May 27, 1893, he graduated from the School of Mines, Columbia University, with a degree in metallurgical engineering in 1915. Mr. French gained his early engineering experience with the American Smelting and Refining Co., serving as a chemist and as-sayer at the company's Murray, Utah, installations. He later returned east and became a metallurgical engineer for the General Vehicle Co., Long Island City, IT. Y., a subsidiary of the General Electric Co. In 1917 Mr. French was appointed civilian inspector of materials for the U.S. Army Signal Corps, and continued this work when it was later absorbed into the Bureau of Aircraft Production. Subsequently he was appointed district inspector in Philadelphia for the Pittsburgh (Ordnance Metallurgical) office, later transferring to Pittsburgh. After World War I Mr. French became an assistant physicist on the metallurgical staff, U. S. Bureau of Standards, Washington, D. C. During his years with the Bureau, he was successively associate physicist, metallurgist, senior metallurgist, and assistant chief, division of metallurgy. In 1929 Mr. French joined International Nickel as a metallurgist at the company's Bay-onne, N. J., research laboratory. Transferring to the development and research division, New York, in 1931, he took charge of alloy steel and iron development, becoming assistant manager of this division in 1943. Mr. French's appointment as an Inco vice president came in March 1947. Previously, he was appointed assistant vice president of the International Nickel Co. of Canada Ltd. in January 1947. Mr. French served the War Production Board during World War II as senior technical consultant in charge of the metallurgical and specifications section of the iron and steel branch. When this section of the WPB was organized into the steel division, he was appointed chief of the metallurgical branch. From March 1944 to September 1945 Mr. French served as assistant director. Herbert French was well known not only for his prolific contribution to the metallurgical literature, for which he received numerous awards, but also for his prolonged service to the profession through its technical societies. He was a past president of ASM, and was the Campbell Memorial Lecturer for that group in 1933. Mr. French was honored by the American Society for Steel Treating in 1931 when he was awarded the Henry Marion Howe Medal. A series of lectures he gave in 1941 before the Fourth Western Metal Congress in Los Angeles was later published in book form under the title Alloy Constructional Steels.

Jan 1, 1957

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By M. H. Merriss

IN THE last few years, there have been developed at the plant of the Nichols Copper Co., Laurel Hill, Borough of Queens, New York City, improvements in electrolytic copper refining by the series system that have materially increased the flexibility and economy of that system. The purpose of this paper is to discuss, as of interest to refiners and to those who have copper to refine, as well as to the engineering profession in general, the changes that have taken place resulting in wider application and increased efficiency of the series system. Copper is electrolytically refined in two ways, which are spoken of as the "multiple system" and the "series system." In both systems, the electrolytic tanks are in series electrically. In the multiple system the electrodes in a single tank are in multiple or in parallel, thus: In the series system, the electrodes in a single tank are in series, thus: There are two important adaptations of the series process, one represented by the series electrolytic tank room at the Baltimore Copper, Smelting & Rolling Co., Baltimore, Md., and the other by that of the Nichols Copper Co.&apos;s plant. At Baltimore, the anode is rolled to perfect

Jan 6, 1925

By G. St. J. Perrott

One of the important hazards in coal mining is the danger of ignition of explosive mixtures of methane and air or coal dust and air, or both, by the explosives used in blasting the coal. It has long been recognized that certain explosives are more dangerous than others in this respect. &apos; In America and abroad, government testing stations have been established for officially passing on the suitability of explosives for use in coal mines. In this country the Federal government is given no power to enforce the use of the approved explosives but merely publishes from time to time, through the Bureau of Mines, those explosives which have passed the tests necessary to place them on the list for use in coal mines. In spite of this lack of police power, the increase in the use of permissible .explosives since the promulgation of the fist list in 1909 has been rapid. In 1912, only 8 per cent. of the explosives used in coal mines were permissible; in 1925, this figure had increased to 25 per cent. While the past record of permissible explosives has been most gratifying, it is very desirable that we pave the way for further improvement in explosives and blasting methods by learning more about the mechanism of ignition of gas and coal dust by explosives. To this end a considerable amount of investigative work already has been carried out and a large amount yet remains to be done. It is the purpose of this paper to discuss briefly the effect of the characteristics of explosives and method of loading in the borehole on the liability of a blown-out shot to ignite explosive mixtures of gas or dust. For an account of the methods by which an explosive is tested for permissibility for use in coal mines, the reader is referred to Schedule 17-A of the U. S. Bureau of Mines. Safety Factor in Using Explosives The factors that affect the liability of an explosive to ignite gas or dust are already known in a qualitative way but quantitative data are

Jan 1, 1927

By Allen F. Agnew

Geologic studies for the Federal and State governments in the Wisconsin-Illinois-Iowa zinc-lead district were begun in 1835, and subse¬quent surveys were made in the three states at in¬tervals until 1916, see Table I. The current study of the district, Fig. 1, by the U. S. Geological Survey was begun in 1942 in the hope that a systematic investigation would help in¬crease production of zinc and lead, then in ex¬tremely short supply. Major emphasis of the USGS program was on detailed mapping of the geologic structure and ore deposits. Preliminary maps and reports covering localities of intensive mining ac¬tivity have been published during the course of this study, Fig. 2. By 1950 the objectives of the study by the USGS were revised; 7Y2-min quadrangles of relatively unprospected localities as well as inten¬sively mined localities are now being mapped in Wisconsin. Since 1945 the investigation in Wiscon¬sin has been made in cooperation with the Wiscon¬sin Geological and Natural History Survey, and since 1951 the geologic mapping of areas of particu¬lar interest in Iowa has been performed in coopera¬tion with the Iowa Geological Survey. At intervals since 1943 the Illinois State Geological Survey has mapped the geologic structure and ore deposits of localities in the Illinois part of the mining district, see Fig. 2.

Aug 1, 1955

By D. Walton, B. Chalmers

A preferred orientation is known to occur frequently in the columnar zone of castings. This has been attributed to a preferred direction of growth. However, no satisfactory mechanism was proposed by which the preferred direction of growth led to the preferred orientation. The purpose of this work has been to establish this mechanism. It has been found that in general the observed preferred orientations only develop when the preferred directions of growth reveal themselves by dendritic growth. A mechanism based on this premise is found to be in agreement with the experimental data obtained in the course of this work. WHEN a liquid metal is allowed to solidify in a mold, it usually freezes in three stages, distinguished from each other by the size and shape of the grains. The first zone to freeze (the chill zone near the mold wall) consists of relatively fine grains that are equiaxed in shape and random in orientation. The next zone consists of crystals that are elongated in the direction of heat flow, i.e., normal to mold wall. These crystals are much larger in cross section than the crystals of the chill zone and have a very strongly preferred orientation. This is the columnar zone. The final zone, which is absent in very pure metals, is again equiaxed and randomly oriented, but usually has a much coarser grain size than the chill zone. The purpose of this study is to describe and account for the crystal size and orientation in the columnar zone. The occurrence of a preferred orientation in the columnar zone is well known, and in 1940, Greninger&apos; suggested that it is apparently related to dendritic growth although at that time the only data were for metals with the face-centered-cubic structure. Table I shows that the direction of dendritic growth and the crystal axis that follows the heat flow direction coincide in all cases so far studied. The term "dendritic growth" is used here to represent the branched type of morphology that is characteristic of growth into supercooled melts.&apos; In addition to the supercooling which is necessary before nucleation will occur at the mold wall, the necessary supercooling for continued dendritic growth can be provided in a mold by heat flow into the already formed solid at an interface whose Liquidus temperature is depressed by an accumula-

Jan 1, 1960

By L. A. Schrider, J. A. Wasson

A method of predicting waterflood performance has been developed that combines certain facets of several previously published prediction techniques. The manner of combination has required the development and use of some new and some little-known relationships and has eliminated several of the weaker assumptions inherent in the original individual prediction methods. This approach, which was designed for computer solution, has removed the necessity of referring to plotted curves and permits the analytical prediction of water flood performance for a five-spot well pattern in either homogeneous or stratified reservoirs. The Predicted values are expressed in common oilfield units rather than in abstract or dimensionless terms. The calculation procedure has been programmed in FORTRAN IV and the entire program listing is available to potential users.* Introduction Prior to initiation of secondary recovery of oil by waterflooding, the possibilities of economic success or failure must be evaluated with the greatest practical accuracy. Although many prediction techniques are available, most, if not all, have serious limitations. In recent years, the Bureau of Mines has attempted to stimulate interest in the secondary recovery of oil from Appalachian pressure-depleted reservoirs. Waterflooding, because of its widespread acceptance and success, is the principal secondary-recovery method considered. During the life of the project, several performance prediction methods have been studied and applied. Because these methods, individually, have inherent assumptions and limi-tations, portions of some of them have been selected and combined in an effort to eliminate such shortcomings wherever possible. We believe that the resulting technique is as accurate as the necessary available data will permit and that it has several distinct advantages over previously published methods. Development of the Method The fractional flow equation developed by Buckley and Leverett&apos; from Darcy&apos;s law is the fundamental mathematical statement describing immiscible fluid-fluid displacement in porous media. A generalized form of this relationship, whose derivation is readily available in the literature, is The formation dip, a, is usually very small in those petroleum reservoirs being considered for pattern waterflooding in the Appalachian area. Therefore. in many cases. a has an almist negligible value. In addition, Ap, the difference between the density of water and the density of oil, is relatively small. For these reasons the gravitational term may often be neglected. Capillary pressure is a function of saturation, which is in turn a function of distance from the upstream boundary of the system or the injection well. In this study it is assumed that the frontal zone of the waterflooding (or zone of capillarity) has negligible length and that only those saturations in the water-swept zone at breakthrough and later are of interest. As the distance in a waterflood pattern is comparatively large and the change in water saturation with distance is usually small, the change in capillary pressure with distance is negligible. The simplified form of the fractional flow equation is appropriate, therefore, in this application. Three variables must be considered in determining that fraction of the total fluid flow that consists of water: the viscosity ratio, saturation, and relative permeability ratio.

Jan 1, 1969

By B. M. Larsen, T. E. Brower

An increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely, that which presumably is present in diffusible form in the solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent Oz in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932