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By R. T. Torgerson, W. A. Baginski

Alloying studies were conducted on modifications of Cb-10W-1OHf (C-129) alloy as part of a cooperative alloy development effort between The Boeing Co. and the Wah Chang Corp. The purpose of these studies was to develop a fabricable, high- strength columbium alloy with superior melding properties. The initial investigations of alloy modifications were conducted using laboratory-melted button ingots. An alloy with the composition exhibited excellent veld ductility, elevated-ternpevature strength, and fabricability. The yttrium-modified alloy was desigrzated C-129Y and was selected for further developrnetzt. Three prodziction heats of C-129Y weve processed into sheet. Welding, forming, and tensile proper-lies are presented for this material. Tungsten-are welds of. C-129Y exhibited a minimum bend radius of 1/2T in the as-welded conditioti compared to 8T for C-129 alloy. An investigation was conducted on Disil coating of C-129Y and test data are presented on oxidation resistance and effects of re-entry environments. The excellent combination of strength, fabricability, weldability, and low transition temperature of C-129Y alloy offers potential design advantages for use of this alloy in structures of aerospace vehicles. It is atiticipated that C-129Y will rapidly supplant C-129 and similar alloys clue to the versatility provided by its impvoved welditzg properties. COLUMBIUM alloys with improved properties are required to achieve better performance and efficiency of radiation-cooled structures for re-entry vehicles and recoverable launch systems. Cooperative work by The Boeing Co. and the Wah Chang Corp. resulted in the development several years ago of C-129 alloy, a high-strength Cb-W-Hf alloy.' This alloy has received favorable consideration for many advanced designs of high-temperature structures due to its excellent combination of properties. However, this alloy exhibits low weld ductility unless given a high-temperature stress-relief treatment. For this reason the development effort was directed towards modification of the C-129 alloy composition (Cb-1OW-1OHf) to eliminate the need for post-weld heat treatment. This paper describes the successful development of an alloy meeting this requirement. This new alloy was designated C-129Y and has a nominal composition of EXPERIMENTAL PROCEDURES Alloying Studies. Various Cb-W-Hf compositions were investigated using are-melted button ingots. These buttons were hot-forged using a protective glass coating and rolled into sheet specimens. Metal-lographic examination: tensile testing, and welding studies were conducted to evaluate properties of the experimental alloys. Sheet Fabrication. Three pilot production heats of C-129Y were fabricated into sheet to establish processing techniques and to determine sheet properties. The three heats consisted of 6-in.-diam ingots weighing from 140 to 250 lb. The ingots were prepared by electron-be am melting followed by vacuum-arc melting. The hafnium and yttrium additions were made during the are-melting operation by tack welding alloy strip additions to the Cb-W master-alloy electrode. The final ingots were machined into billets with samples of the machine turnings collected for chemical analysis. Ingot breakdown methods for the three heats are as follows: Ingot Ingot Heat Size Weiaht___Breakdown Method A 6 in. 250 lb Hot extrusion B 6 in. 140 lb Hot forging C 6 in. 250 lb Hot extrusion Sheet bars from the extrusion and forging operations were conditioned, recrystallized, and rolled into sheet. Initial rolling was conducted at elevated temperatures and final rolling was conducted at room temperature.

Jan 1, 1967

By J. C. Yannopoulos, N. J. Themelis

Ah electronic thermogravirnetric balance was used to measure the veductioiz rule o single cirpric oxide particles suspended in a stream of hydrogen. Very jzne thermocouples embedded in lie center and at the surface of the sphere recorded the variation of terw perature during reduction. In contrast to iron oxide reduction, where in most instances the rate of interface reactiokl is controlling, the heat- and mass-transfer phenotnena play a predolrinant role in the reduction of cupric oxide. The correlation of experitnental data or tnass lransfev lhrough the boundary layer at Reynolds nunlber 0-4 50 was as jollocs: ThE reduction of cupric oxide by hydrogen is represented by the equation: It is a highly exothermic reaction and the amount of heat released varies only slightly with temperature (-21,430 cal per g-mole at 400°C). Most of the published studies on this system have been conducted at temperatures in the range of 34 to 280c.l-&apos; The concensus of opinion has been that at temperatures below 200°C the reaction is preceded by an induction period during which there is very little or no reduction. The length of this period diminishes as the temperature of the reaction is increased1l5 and aseawa found that at 280°C reduction starts practically immediately when the oxide is exposed to hydrogen gas. The existence of an induction, or incubation, period has led experimenters to believe that the reduction of CuO by hydrogen is catalyzed by metallic copper.&apos; Boldurev and rmolaev found that mechanical additions of powdered copper to oxide did not affect its reduction, although metallic copper produced during the reduction seemed to have a catalytic effect. At least three other authors2&apos;5&apos;7 have reported that addition of copper had no effect on the rate of reduction. Pease and alor&apos; observed that water vapor had a strong inhibiting effect on the reduction at 1503C, but its effect was greatly diminished at 200 C. Pavlychenko and Rubinchik5 studied this reaction at 159 to 235 C and found that, once the reaction had been initiated, there was no inhibiting effect due to the introduction of water in the hydrogen stream; at temperatures above 183°C there was no inhibiting effect due to water vapor, either before or during reaction. The same authors noted that the rate of reduction was independent of pressure in the range of 200 to 700 mm Hg. aseawa investigated the kinetics of the CuO-Hz system at 160 to 280°C and estimated the apparent activation energy at 14,000 cal per g-mole. A similar value (13,500 1200 cal per g-mole) was reported by ond&apos; in the temperature range 148 to 216°C. Bond also reported that there was no incubation period and that water vapor had no inhibiting effect on reduction at temperatures above 190 C. The above studies have been conducted at temperatures below 280°C and the physical configuration of the system under investigation has not been defined adequately. However, it is well-known that the mechanism of gas-solid reactions depends on a number of in series physical and chemical rate prcesses.&apos;&apos; It is, therefore, essential to include among the experimental factors the geometry of the solid system and the mass-transport characteristics of the reducing gas. Scott studied the reduction of packed beds of cupric oxide cylinders by Hz-He streams of very low hydrogen concentrations at temperatures 400 to 600 C, pressure of 10 to 30 atm, and gas velocity from 0.18 to 5.8 ft per sec (3 < Rep < 30). The reduction rate was found to be mainly controlled by diffusion through the boundary layer and through the pores of the reduced copper phase. The following correlation was proposed: Scott in an earlier work studied the reduction of fixed beds of cupric oxide wire and found that the rate of flow of the gas stream through the bed had a controlling effect on the rate of reduction. The same mass-transfer phenomenon was observed by Bond and clark13 on a similar reduction system. The analogy between mass and heat transfer through the boundary layer which exists between a solid surface and the bulk stream stems from the similarity of the differential equations representing these phenomena

Jan 1, 1967

By J. L. Huitt, S. R. Darin

The use of a partial monolayer of propping agent to obtain a high flow capacity for a hydraulically induced fracture is discussed. From the results of laboratory work it was shown that a modified form of the Kozeny-Carman relation could be used to describe the flow in the partial monolayer propped fracture. With equations presented in the paper, the density pattern of the propping agent (number of particles per unit of fracture surface) that results in the maximum flow capacity for the fracture can be determined. The maxitnum flow capacity obtained with a partial monolayer is often an order of magnitude greater than the flow capacity obtained in greater width fractures containing multilayers of the propping agent. INTRODUCTION One of the predominant factors controlling the success of a hydraulic fracturing operation is the propping of the fracture. The trend in hydraulic fracturing recently has been an increase in the ratio of propping agent-to-fluid. The primary purpose of this increased ratio is to sustain a propped fracture of greater width. It was shown in a recent study&apos; that for some formations low concentrations of propping agent would result in "closing" or "healing" of the fracture. In some cases, in an effort to insure sufficient propping agent concentration, the fracturing operation is designed to obtain a pack of the propping agent in the fracture. The placing of a pack of propping agent in the fracture provides a fracture of maximum width; however, the width alone does not control the flow capacity of the fracture. The flow capacity is dependent on the permeability of the fracture, as well as the fracture width. Thus, increasing the permeability to obtain larger flow capacities is as important as obtaining a greater width fracture. By increasing the concentration and particle diameter of the propping agent, fractures of sufficient flow capacities are obtainable for effective well stimulation in a number of formations. However, in some of the recovery techniques, the fracture capacity obtained by commonly used practices in fracturing is inadequate. One such recovery technique is gravity drainage via a horizontal fracture placed near the base of the productive zone. For this recovery technique, the fracture capacity desired is usually one to two orders of magnitude greater than the fracture capacity normally obtained in fractures propped with the size of sand commonly used (20-40 mesh). By the use of particles of larger diameter, the permeability of a pack2 is increased; however, even a multilayer pack results in a fracture flow capacity lower than that desired for some formations. For example, a fracture of 1/4-in. width, packed with 8-12 mesh sand of about 2,000 darcies permeability, would result in a fracture flow capacity (permeability X fracture width) of only 40,000 md-ft. If the fracture flow capacity needed is an order of magnitude greater than that cited in the example, an approach different from the formation of a pack in the fracture is needed. One approach is a partial monolayer of large-diameter propping agent. In working with this type of fracture system, it was found that the flow problems were unique to the system; therefore, the study discussed in this paper was made. THEORY AND RELATED STUDIES Previous studies, although related to that described in this paper, have not pertained directly to the flow in a fracture propped with a partial monolayer of propping agent. However, studies such as flow between parallel plates,&apos; flow in packed columns,&apos; fracture flow capacity&apos; and flow in simulated fractures reduce the scope of this flow problem considerably. A fracture propped with a partial monolayer of dropping agent may be considered to be between two extremes — between an open fracture and a bed of particles packed In a conduit of fracture geometry. Thus, it seems appropriate to review the extreme cases.

Jan 1, 1967

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,&apos;who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

By P. G. Shewmon

Radioactive MgZA has been used to study the rate of self-diffusion in oriented single crystals of magnesium in the temperature range 468O to 635OC. The diffusion coefficients parallel and perpendicular to the c-axis are: Dl, = 1.0 exp (—32,200IRT) cm2 per sec and Dl = 1.5 exp (—32,500IR T) cm Qer sec. The ratio Dl/Dll was found to vary from 1.13 at 468 to 1.24 at 575 C. Assuming a vacancy mechanism, an explanation of this aniso-tropy of diffusion follows from a consideration of the difference in the saddle points for diffusion in and out of the basal plane. RECENT discovery of radioactive Mg2"&apos;-&apos; has made possible the study of self-diffusion in magnesium. The experimental procedure and the results of a study of diffusion in polycrystalline magnesium have been described in an earlier paper.V he present work is an application of the same techniques to the study of self-diffusion in oriented single crystals of magnesium. In the general diffusion problem the diffusion coefficient is a second order tensor relating the two vectors, the diffusion flux, and the concentration gradient. In a hexagonal lattice, such as magnesium, the complete determination of the diffusion coefficient D as a function of direction in the lattice requires a knowledge of D,, and D,, i.e., the diffusion coefficients parallel and perpendicular to the c-axis, respectively. It can be proven quite generally that in a hexagonal lattice D is independent of direction in the basal plane, and that out of the basal plane it varies with 0, the angle between the c-axis and the direction of diffusion, according to the equation D(B) = D,,cos2B + D,sin2B. [I] The proof of Eq. 1 depends only upon the symmetry elements of the hexagonal lattice and upon the transformation properties of a second order tensor." Therefore, Eq. 1 holds for any mechanism of diffusion and any c/a ratio. Experimental Procedure The experimental procedure used with polycrystalline specimens can be briefly outlined as follows. Radioactive Mg" was produced by bombarding a NaCl crystal with 350 mev protons and was chemically separated from the target as MgO. The Mg" was then vapor deposited on a specially cleaned magnesium specimen by heating the MgO on a tantalum ribbon in a vacuum. During the diffusion treatment, oxidation and vapor loss of the radioactive material were minimized by annealing the samples in pairs with the active faces in contact, each pair being inside a magnesium container, which was in turn surrounded by an argon atmosphere in a sealed Pyrex tube. The distance-activity profiles were obtained by measuring the activity of thin sections cut parallel to the original interface with a lathe. The only technique which was peculiar to this work was the preparation and orientation of the single crystal specimens. The single crystals used in this work were grown by E. C. Burke of the Dow Chemical Co., using a modified Bridgman method, in which the furnace and specimen were stationary while the temperature gradient moved.&apos; In growing these crystals the starting material was distilled magnesium, the crucibles were machined from Acheson electrode graphite, and the furnace atmosphere was tank argon. The crystals were grown from sublimed magnesium with the following analysis: 0.0002 pct Al, 0.0017 pct Fe, 0.0009 pct Mn, 0.0001 pct Ni, 0.0006 pct Pb, and less than 0.01 pct Ca, 0.0001 pct Cu, 0.001 pct Si, 0.001 pct Sn, and 0.02 pct Zn. The two crystals used were roughly lh in. diam and eight in. long. The c-axis made angles of about 7" and 78", respectively, with the specimen axes. If the values of D obtained by the use of these two crystals are taken equal to D,, and D,, respectively, the error introduced by this assumption is less than 1 pct. This can be shown by combining Eq. 1, the identity sin% + cos&apos;8 = 1, and the experimental fact that DJDn in magnesium was always less than 1.25.

Jan 1, 1957

By L. H. Reiss, J. Groult, L. Montadert

Many fields, where the reservoir is composed of sandy layers, show great complexity because of the lack of continuity which results from a particular type of seditnentation. This complexity may be a factor of prime importance in studying reservoir drainage, especially in the displacement of oil by water or gas. This paper describes work done to study this heterogeneity and its influence in the exploitation of the fields of the lower Devonian sandy shale in the Fort Polignac Basin in Algeria. Two lines of research were followed. 1. On the border of the hasin, a detailed sedimentological study established rules for the distribution of the sandy zones, which furnished hypotheses necessary for devising a geologic model of the reservoir. A certain number of sandy zones were recognized and characterized by their sedimentation. 2. In the interior of the basin, production logs deterrnined the productivity profile. Study of these point data led to a description of the distribution of oil and gas phases in the reservoir so that the continuity of different zones between the wells could be deduced. These techniques were applied to the study of the lower Devonian sandy shale reservoir of Zarzaitine. The sedimentological study guiding the correlation work, with the aid of the conventional static data (logs and cores), led to the establishment of a useful geologic model of the reservoir. Production logs, thanks to the contribution of dynamic elements, permitted corrobora-tion of the model. In particular, the logs confirmed separation, as proposed by the sedimenfological study, of two comparable sandy groups by revealing the continuity of a thin impermeable layer, invisible on conventional logs. INTRODUCTION The heterogeneity of sandstone reservoirs considerably influences the distribution of fluids, as well as their displacement in the reservoir. Rational development of a field and maximum recovery of hydrocarbons are closely tied to an exact and precise knowledge of the intern architecture. We will try to show how it is possible I refine the knowledge of the reservoir by seeking qui different and varied sources of information. Productic geology, the group of techniques which leads to idei concerning reservoir architecture and its geometric descris tion, furnishes the framework of this undertaking. Of these techniques. those used so far are qui varied. Descriptive as well as quantitative, the technique partake as much of classical geology as of reservo science. They include (1) geologic studies of the enti basin, especially a stratigraphic and sedimentologic study of the reservoir member at its outcrop, detail1 observations of cores taken from wells and, finall oriented cores; (2) interpretation of geophysical dat (3) interpretation of electric logs, nuclear and sonic lo and dipmeters: (4) petrophysical study of the reserve on samples taken from wells; (5) reservoir dynamics (stu of the production history and, in particular, interpretati of production logs); and (6) analysis of the fluids a thermodynamic studies. This incomplete list could also include (1) study the migration of the fluids, (2) geochemistry (chemi characterization of the oils), (3) regional hydrodynamii and (4) injection and detection of tracers. If most of these techniques are classic, attention i nevertheless be called to applying two of the techniql in conjunction: the study of the reservoir member its outcrop and the study of dynamic distribution fluid phases in the reservoir through use of product logs, used in the study of the sandy shale reservoirs the lower Devonian of the Fort Polignac Basin, Alge in particular, their application to the study of the 2 zaitine field where they have led to a new and satisfact model of the reservoir will be described. THE ZARZAITlNE FIELD Situated in the interior of the Fort Polignac 8 about 150 kilometers (km) north of the lower Devol outcrop, the Zarzaitine Devonian oil field was discovc On Ian. 28, 19&apos;&apos; (Figs. 1 and l8). It is in the fern a monocline truncated by two perpendicular fault: great throw, with a downthrown section to the north\: Erosion at the top of the structure has caused one of it to disappear. It is a reservoir with a gas cap an m coefficient on the order of 1:5, open to the aql On the northeast, with the oil zone covering an Of 106 sq km and with initial oil reserves of 222 mi

Jan 1, 1967

By R. E. Zimmerman

Wide attention is being placed upon various methods for cleaning the fine sizes of bituminous coals. The author describes and analyzes the results achieved on wet concentrating tables of modern design on unclassified feeds of --1/2 in. particle sizes, including tests on high-sulphur coals.

Jan 9, 1950

By J. E. Burke

Recent investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers 1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen. Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: D = Ktm [,] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Wa1ker4 finds that, in alpha brass) the rate of growth falls off more rapidly than indicated by Eq i after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker&apos;s data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: ] where h and tz are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck3 The results obtained by Beck Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and HuV ater demonstrated expcrimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,io Making implicit use of this assumption, several authors14,16 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parkerg have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary7 are on the average more surromded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1949

Jan 1, 1894

By Anwar-ul Karim

In one of our recent papers, Cheng, Karim, Langdon, and Dom1 analyzed the creep mechanisms in a Fe-4 pct Si alloy. The experimental results of apparent ac-

Jan 1, 1970

Jan 1, 1963

Jan 1, 1970

By D. E. Etter, J. E. Selle

The Pu-Ce phase diagram was determined by differential thermal analysis, metallography, and elechm-nricroprobe analysis. The dingram is chararterized by a eutectic with extensive solid solubility in the cubic Phases of both cerium and plutonium. No intermediate phases were found. Cerium is soluble in e plutonium to 16.0 at. pet Ce at 626OC nnd in d plcltoniurn to 23.0 at. pet at 613 "C, decreasing to 17.5 at. pet at room temperature. No solubility in the a, ß, or ? phases was jound, and the mininum cerium required to stabilize 5 plutonium to room temperature is 3.2 at. pet. The maximum solubility of plutonium in 6 cerium is 19.5 at. pet at 721OC, and the maximum soluhility of plutonium in ? cerium is 34.5 at. pet. Invariant points in the system are: a) eutectic at 626oC, L16.5 = E Pu16.0 + y Ce65.5; b) peritectoid at613oC, e Pu13.5 -y Ce65.5- d Pu23.0. AS part of a program aimed at the determination of the phase equilibria in the Pu-Ce-Cu ternary system, preliminary investigations were made of the three binary systems. A survey of the Pu-Ce binary system by differential therma1 analysis indi- cated several areas of disagreement with the published diagram,&apos; primarily in the shape of the liquidus surface. Consequently, a thorough investigation of the system was undertaken, and this report presents the results of the study. EXPERIMENTAL PROCEDURE Three methods of investigation were used: differential thermal analysis (DTA), metallography, and analysis with electron-microprobe X-ray analyzer (EMX). The EMX analysis was particularly useful for the determination of solvus lines. The DTA method was most useful for the determination of the liquidus curves. Metallography complemented both of these techniques. Materials. The cerium metal used for most of this work had a freezing point of 805°C. This material showed 15°C premelting, and was found metallographically to contain some unidentified in~lusions.2 The temperature of premelting is defined as the point at which the DTA curve breaks away from the base line, analogous to a curve obtained from a solid-solution alloy. Several compositions were prepared near the cerium end of the diagram with higher-purity material which had a freezing point of 800°C. etallographic analysis showed this material to be relatively free of inclusions and only 8°C premelting was observed. Major impurities were found by spectrographic

Jan 1, 1964

By Enrique Touceda, Henry M. Howe

This paper gives the composition of the iron and slag at different stages in the " air-furnace" process of preparing " hard metal," or white castriron, for conversion into malleable cast-iron by annealing. The details of the process are given in an appendix. One of us had been trying for years to work some chemist of some of our malleable-iron plants up to a degree of enthusiasm which would lead him to make such an investigation. It would have had the advantage of the greater familiarity with the conditions which one habitually on the spot must have. Failing in this, he made use of an opportunity which presented itself of taking samples here represented, with such fairness as the conditions permitted, holding firmly that a rough approximation to the truth is better than the complete lack of data, or that a bird in the hand is worth two in the bush. We hope that this attempt may stimulate others effectively to duplicate this work, and thus correct or confirm it. Our results are shown in Table I. and graphically in Figs. 1 arid 2. Discussion.—At the time when the first two samples were taken, the metal and slag were still too sluggish to permit fair sampling, and not until sample 6 were the conditions really favorable, because at the time of the fourth sample the metal was not fully melted, and even at the time of sample 5 it was still sluggish. Indeed, the slag was probably very heterogeneous throughout, because it took up silica and alumina rapidly from the bottom, and because it was so siliceous as to be sluggish at this relatively low temperature. This hetero-geneousness is exaggerated in the two samples of slag 8, apparently by the great viscosity due to its extraordinary acidity. Note that the manganous oxide of one sample is about two and

Jan 1, 1909

P. L. Pratt (University of Birmingham, Birmingham, England)—The author has measured the hardening effect of isolated edge and screw dislocation boundaries in a remarkably elegant manner, and he proposes that the detailed structure of the boundary determines its effectiveness as a barrier to slip although "there are still unknown details of the distribution which may be extremely important." On p. 678 the author states "that for a good crystal (one having a yield of about 30 psi) a change in annealing temperature from 300" to 400 °C resulted in a negligible shift in the level of the stress-strain curve." Is this in agreement with the results of the earlier paper by Li, Washburn, and Parker8 in which such a change of temperature produced notable hardening in crystals with a yield of about 30 psi? Or were these earlier crystals, of the same nominal purity, less perfect than those used in this work? The experiment illustrated in Fig. 15, p. 681, shows that the boundary has sharpened after annealing at 400 °C, the temperature at which the hardening effect first becomes apparent. Did the author verify that no sharpening of the boundary occurred at, say, 300 °C where no hardening was found? This would seem to be an important check on the proposed mechanism, especially since zinc of this purity should polygonize at temperatures well below 400 °C within the annealing times used here. There seem to be at least two alternative explanations which could fit these facts: 1—The boundary may sharpen at 300 °C or even lower temperatures but be unable to contribute greatly to the hardening until jogged by thermal vacancies and other impurity atoms after 400 °C anneal. This mechan- ism, discussed in the earlier paper,&apos; is believed to account for the thermal hardening observed by Blank&apos;" in NaCl, as stated elsewhere: and by results from recent experiments which tend to confirm this view. 2—The dislocations in the diffuse boundary may be locked by impurity atoms at 300 °C and thus only sharpen the boundary at 400 °C with the aid of thermal vacancies. In this case it would be difficult to distinguish between the two sources of hardening (sharpening or jogging), using metal of this purity. Jack Washburn (author&apos;s reply)—The author wishes to thank Dr. Pratt for his discussion. In connection with his first comment, it should be pointed out that the temperature of testing in the present series of experiments was —196°C, whereas, in the earlier experiments he referred to,&apos; it was 20°C. Therefore, the yield values should not be directly compared. It is likely that the crystals used in the present work were initially more perfect macroscopically than the large shear specimens used previously. The small size of the test section in the kink specimens made it possible to select regions of the large crystals, from which they were acid-cut, that were free of observable small angle boundaries. The sharpening of a microscopically diffuse boundary such as that in Fig. 15 begins in zinc of this purity well below 300°C. However, it is probably not justified to conclude that because a boundary looks sharp under the microscope it has attained the ideal structure. The author agrees with Dr. Pratt that jogging of dislocation lines is one of the structural features of a small angle boundary that should be important in determining its strengthening effect. More detailed information concerning the changes in boundary structure as a

Jan 1, 1956

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth&apos;s crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken&apos;s method1&apos; for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.&apos; This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By R. E. Grace, H. W. Schadler

DARKEN1 has established the theoretical relation between the self-diffusion coefficients and the Boltzmann-MatanO Or interdiffusion coefficient: D is the Boltzmann-Matano or interdiffusion coef-

Jan 1, 1960