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By T. M. Morris

R. T. Hukki (Finland Institute of Technology, Helsinki, Finland)—Two schools of thought are developing concerning the order of the rate of flotation. The paper by Morris is intended to show experimental evidence in favor of the first order rate. Arbiter, on the other hand, has presented an earlier paper" to demonstrate the validity of the second order rate equation. Unfortunately his method of plotting is open to criticism, as pointed out by Morris." A more sensitive method of plotting has been described by the writer,= whereby the data presented by Arbiter demonstrate the superiority of the second order plot. The general rate equation may be written in the following forms for the integrated first and second order equations: (A) t = -1/k In Co-R/Co (first order) [4] 1 (B) 1/t = - kCo + kCo2 1/R (second order) As a first approximation the value of Co may be taken as a unity, 100 pct or 1. Whether or not this is the case in all tests performed by Morris is impossible to judge, owing to the fact that the flotation times are extremely short, e.g. 150 sec in tests A. It would, indeed, be very interesting to know what the total recovery R would be after 1 hr of flotation, for example, instead of after 150 sec. Certainly there are circumstances when C, approaches unity within a very small margin of error. Morris has used the same approximation in his example D "since the feed to this cleaner

Jan 1, 1954

By Roswell Johnson

THE prevailing system of wells on a rectangular basis, as shown in Fig. 1-A, has developed because of the exigencies of offsetting at boundary lines. When, however, a very large tract is, being drilled, it is often possible to abandon this inferior method for the superior arrangement C- PROPER STAGGERING FIG. 1.-THREE SYSTEMS OF SPACING WELLS. known as "staggering," which is illustrated in Fig. 1, B and C. The advantages of the triangular over the rectangular method are evident from Fig. 2, computed on the basis of one well to 10 acres (4 ha.). With the triangular system, no land is more than 409.4 ft. (124.8 m.) from a

Jan 8, 1918

By W. C. Hardy, B. W. McArthur

The purpose of this work is to show application of laboratory data in calculating solution gas-drive performance of the Cisco K-I reservoir. Included herein is a diagram showing the graphical relationship between six variables common to all solution gas-drive mechanisms. With an iterative process one may assume existence of any of these six variables at a particular pressure and calculate the production performance likely to occur in a reservoir produced by solution gas drive. Four unique pressure values are described at which the material balance equation alone is sufficient to predict the cumulative volumes of gas produced. Information derived from these pressure points establishes a criterion for determining compatibility of the pressure-volume-temperature (PVT) analysis of the produced crude with the gas production history. Two averaging procedures are used to arrive at a relative permeability-saturation relationship which describes the field-wide performance. INTRODUCTION The Cisco K-1 reservoir is a lenticular-type sand structure lying at approximately 6,300-ft subsurface. It is located in the H. and T. C. Railroad Co. Block 97, SW 1/4 S 392 and NW 1/4 S 385, Scurry County, Tex. Correlation of data from logs indicated that the Cisco K-1 reservoir occupied approximately 3,218 acre-ft of space with a closure of from 15 to 20 ft. Analysis of the production data indicates that the initial formation pressure and temperature were 2,450 psig and 121°F, respectively. The bubble point occurred at 1,715 psig after production of 12,256 STB oil and 11,520 Mcf gas. Only traces of water have been produced since initiation of production. Successive material balance calculations from June, 1952, to June, 1957, showed that no initial gas cap or water influx has contributed to production of oil and that the Cisco K-1 reservoir originally contained approximately 1.44 X 10" STB of oil. THEORY Methods for calculating solution gas-drive perform-

By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By R. W. Kraft

A comprehensive analysis of the crystallographic and metallographic structure of several Al-CuAl, lamellar eutectic grains solidified under equilibrium conditions has been performed. A consistent pattern was discovered which was interpreted in terms of a detailed atomistic model of an interface describable as: Interface II {111} AL 11 {211} <101>Al <120> ? Several arguments are presented to substantiate the theory. It is compared in detail with another interface model characteristic of the Wid-manstatten precipitate of CuAl2 in A1 at low Cu levels. In addition, a concept is proposed to help explain the structure of the compound CuAl2. It has been shown that the eutectic alloy between A1 and CuA1, can be forced to solidify as substantially parallel lamellae throughout a relatively large volume&apos; by appropriately controlling the solidification parameters of growth rate, thermal gradients, and impurity level and by causing solidification to proceed in a unidirectional fashion from one end of an ingot to the other. A typical ingot solidified in this manner shows three distinct zones along the length of the ingot, Fig. 1. At the head end is a region consisting of many different grains, some of which are elongated slightly in the direction of solidification. After a few centimeters of growth, this polygrained region gradually merges into the second zone which consists of a very few elongated coarse grains. The third zone at the tail end is a region of eutectic colonies caused by segregation of impurities. Microscopic examination of transverse and longitudinal sections of the ingots reveals that during the initial stages of growth (zone I) the lamellar structure is frequently highly distorted and twisted but that it straightens out in zone 11. This characteristic pattern suggests that nucleation of a eutectic grain begins randomly at the head end of the ingot, and that some particular orientation relationship between the phases is more favorable from an energy consideration than others for one reason or another, so that some grains grow and others which are less favorably oriented do not. The favorably oriented or "low energy" grains continue to grow until excess solute rejected at the advancing liquid-solid interface destroys the parallel lamellar structure by forming a cellular rather than a substantially planar interface. When this occurs, the parallel lamellae fan out and eutectic colonies are formed because the lamellae grow perpendicular to the local interface. Questions naturally arise as to the crystallographic nature of the "low energy" grains. What do the grains which persist into zone II have in common? Can this explain the stability of such grains during growth? To answer the first question it is necessary to determine the crystallographic orientation of the lamellae of each phase relative to one another. This has been done for Al-CuAl2 eutectic alloys by two different techniques on specimens prepared in different ways.2&apos;3 The results were different from each other and from a third orientation relationship between A1 and CuA1, reported for overaged A1-Cu alloys.4 The three orientation relationships are summarized below to illustrate their similarities and their differences. (001) ? 11 (001) A1; [l00] ? 11 [l00] Al Eutectic, Ref. 2 (001) 8 1) (001) A1; [1001 ?11 [1101 A1 Eutectic, Ref. 3 (001) ? 11 (001) A1; [l00] ? 11 [310] Al; Widmanstfitten, Ref. 4 It is not surprising that different orientation relationships were found by Ellwood and Bagley,&apos; and Takahashi3 since the solidification conditions were quite different. Nor is it surprising that Mehl, Barrett, and Rhines 4 found still another value since they were studying another type of alloy. Nevertheless, it would be expected that some logical and systematic pattern could be found if all the alloys were at equilibrium since the same two phases are

Jan 1, 1962

By C. H. Li, R. J. Stokes, T. L. Johnston

A portion of the Ni3Cr-Ni3Al phase dzagram has been investigated, including the precipitation of 1 (Ni3Al) as well as the existence of ordered Y (Ni matrix), Extensive metallographic studies by electron microscopy have been carried out and X-ray diffraction diagrams have been taken at both elevated and ambient temperatures, No long-range ordering of the phase was found above 893°C (1639°F) in the compositional range investigated. The high rate of formation of the ordered ?1 phase upon quenching has been confirmed, a phenomenon which up to the present Lime has retarded the understanding of this phase diagram, Specimens with controlled amounts of ?1 exhibited up to a six-fold improvement in yield and creep strength compared with single-phase Ni-Cv-A1 alloys. MOST of the important high nickel heat-resistant alloys are related to the nickel-chromium-aluminum system. One of the important functions of the aluminum, often accompanied by titanium, is to produce a precipitate of the very fine ?1 phase (Ni3A1, X) where X may be Ti, Cr, or other elements. A number of investigators1-" have demonstrate the presence of y&apos; in these alloys but most of their materials contained large amounts of other elements resulting in appreciable amounts of con- fusing phases such as carbides. Further clouding of the precise role of y&apos; has been the suspected existence of an ordering reaction in the y matrix itself, ro-3,12-17 It appeared from these investigations that aluminum in Ni-Cr alloys would raise the ordering temperature of the matrix from 540°C at NisCr to 1300°C at Ni,Al. In support of this possibility, the matrix phase in the parallel Ni-Fe-A1 system is ordered to very high temperatures.1 OBJECTIVES OF THIS RESEARCH From this survey of the literature it appeared desirable to conduct an investigation of the simple Ni-Cr-A1 system using the alloys of the highest available purity to avoid the complication of foreign phases and thereby isolate the structures in the Ni-Cr-A1 system. Procedures were developed to study ? - ?o and ? - ?1 equilibria. Preliminary mechanical tests at elevated temperatures were also conducted.

Jan 1, 1962

By EDBIUND U. NORTH

IN making a glass model of mine-workings, each mine will present some little individualities, to meet which will call for the exercise of special ingenuity. Having made several models, I offer the following details of the model of the Montana-Tonopah mine-workings, believing that with small changes for different conditions the method described can be successfully used in making a glass model of the workings of any mine. The model, Fig. 1, has the top, one end, and the front removed. The case is made of kiln-dried pine, painted with several coats of dead-white paint. It is made to take sheets of glass 24 by 42 in. in size, and is 18 in. high, the workings shown being on a scale of 1 in. = 40 ft., or 4800 : 1 scale. The base is made of four pieces of 2-in. material, well pinned and glued together. The back, of material 1 in. thick, is secured rigidly to the base by screws and countersinking. The four posts, 1.5 in. square, are so cut that. the front and two ends of the model fit in flush with the outside edges of the posts. The top rails, 1 in. square, are fastened rigidly to the front and back posts by means of small iron braces. The ends, front, and top of the case are of 0.5-in. material; the ends and front are held in place at the bottom by pegs fitting into the base ; at the top the ends are held by buttons and the front by cupboard-hooks on the inside. Hinged hasps on the cover, fitting over staples in the end-pieces, make it easy to lock the entire case. Before the back is fastened to the base, it is cut with horizontal and vertical grooves to receive the horizontal and vertical sheets of glass, shown clearly in Figs. 1 and 2. The horizontal grooves, spaced to scale, represent the vertical distances between the levels at the shaft. The vertical grooves are placed wherever cross-sections of the workings are desired.

Jan 1, 1910

By Edmund D. North

In making a glass model of mine-workings, each mine will present some little individualities, to meet which will call for the exercise of special ingenuity. Having made several models, I offer the following details of the model of the Montana-Tonopah mine-workings, believing that with small changes for different conditions the method described can be successfully used in making a glass model of the workings of any mine. The model, Fig. 1, has the top, one end, and the front removed. The case is made of kiln-dried pine, painted with several coats of dead-white paint. It is made to take sheets of glass 24 by 42 in. in size, and is 18 in. high, the workings shown being on a scale of 1 in. = 40 ft., or 4800 : 1 scale. The base is made of four pieces of 2-in. material, well pinned and glued together. The back, of material 1 in. thick, is secured rigidly to the base by screws and countersinking. The four posts, 1.5 in. square, are so cut that the front and two ends of the model fit in flush with the outside edges of the posts. The top rails, 1 in. square, are fastened rigidly to the front and back posts by means of small iron braces. The ends, front, and top of the case are of 0.5-in. material; the ends and front are held in place at the bottom by pegs fitting into the base ; at the top the ends are held by buttons and the front by cupboard-hooks on the inside. Hinged hasps on the cover, fitting over staples in the end-pieces, make it easy to lock the entire case. Before the back is fastened to the base, it is cut with horizontal and vertical grooves to receive the horizontal and vertical sheets of glass, shown clearly in Figs. 1 and 2. The horizontal grooves, spaced to scale, represent the vertical distances between the levels at the shaft. The vertical grooves are placed wherever cross-sections of the workings are desired.

Jan 1, 1910

By John R. Hutchins

1ms is a report of nickel (wire) oxidation studies designed to test the validity of Valensi&apos;s1 equation developed for the kinetics of a reaction controlled by diffusion in a continuously growing product layer on cylindrical surfaces. The equation is:

Jan 1, 1968

By Harold Margalin, Elmars Ence

M. H. Mueller, M. V. Nevitt, and H. W. Knott (Argonne National Laboratory)—We have reported1 the crystal structure of Ti2CU as body centered tetragonal with a. = 2.944A and co = 10.786A, six atoms per unit cell, and space groupl4/mmm(MoSi2 type). This cell is larger but definitely related to the unit cell reported by the authors. It permits definite positions for the titanium and copper atoms in the cell located as follows: 2 Cu (a) 0 0 0; 1/2 1/2 1/2 4 Ti (e) 0 0 z; 1/2 1/2 1/2 + z; 0 0z; 1/2 1/2 1/2- z where z = 0.341 The face centered tetragonal cell reported by the authors can be transformed to a small body centered tetragonal cell with flo (small bet) = ao(fct)v2 Both unit cells have the same CO. Neither the face centered tetragonal cell with four atoms per unit cell nor the small body centered tetragonal cell with its two atoms per unit cell lend themselves conveniently to an orderly arrangment of the 2 to 1 ratio of titanium to copper atoms. When the co of this small body centered cell is tripled, however, a large body centered tetragonal cell results with six atoms per unit cell as described above. We had also noted that the X-ray patterns of Ti2Cu indicated that the structure could be approximately described by the face centered tetragonal cell as reported by the authors; how- ever, there was evidence for a few additional very weak lines whose positions indicated a larger unit cell. Since the X-ray scattering amplitudes of titanium and copper are nearly equal, it is evident that it is difficult to distinguish their positions especially from X-ray powder patterns. It was therefore decided to look at a powder pattern obtained by neutron diffraction since the scattering amplitudes of the two elements are considerably different in magnitude and opposite in sign. The sample used for neutron diffraction was selected from a group of three alloys prepared by arc melting using crystal bar titanium of 99.92 pet nominal purity and 99.999 pet pure Cu. The alloys designated as A, B, and C had the following respective compositions: Ti-32.8 at. pet Cu, Ti-33.3 at. pet Cu, and Ti-33.8 at. pet Cu. On the basis of the melting losses incurred, it was established that the actual concentration of either component in any of the alloys probably did not deviate from the intended value by as much as 0.1 at. pet. The alloys were annealed for 5 days at 700°C in evacuated Vycor capsules and quenched in tap water. The metallographic structures of these alloys are shown in Fig. 1. None of the alloys contained sufficient second phase to permit its positive identification. Since alloy B contained the least amount of second phase and since its composition placed it closest to the ideal stoichiometry, it was chosen for the neutron diffraction study. The oxygen content of alloy B was found by chemical analysis to be 0.06 at. pet. This particular intermetallic compound is especially suitable for investigation with neutron diffraction since if the titanium and copper atoms have a random statistical distribution, a near null-matrix would result in which there would be practically no coherent scattering of neutrons, and hence no Bragg diffraction peaks. Such a condition could come

Jan 1, 1962

By M. D. Banus, M. B. Bever, A. K. Jena

Measurements of the heat effects on addition of various solid phases of InSb to a solution calorimeter have confirmed the existence of a new high-pressure plzase InSbQII), which was jormed at 37 kbar and 623°K. The heats of formation of InSbQ), InSbfl), and InSb(111) have been measured and the heats of transjormation of InSb(1) to InSb(1l) and InSb(Iii) and of &apos;InSb(ll) to InSb(iiI) at atmospheric pressure and 78°K have been determined independently. Other thermodynamic properties of these phases, the phase boundary InSb(i)/InSb(ll), and the relative positions of the triple points are calculated. The pressure-Dolume term is shown to be more critical than the internal energy difference in making the phase InSbQ) less stable than InSb(II) at high pressures. Observations on partially transformed specimens suggest that the transformation of&apos; metastable InSb (III) takes place in the two steps InSb(lll) — InSbQI) and InSbQI) — InSb(l). The compound InSb can exist as several phases depending on the temperature and pressure. The phase InSb(I), which is a semiconductor having the zinc-blende structure, transforms into the phase InSb(11) at a pressure of about 23 kbar and room temperature.&apos;-3 The phase InSb(II) has the 6 tin structure,4-6 is metallic, and becomes a superconductor below 2.lok7 An orthorhombic phase of InSb has been reported to occur above a pressure of approximately 30 kbar at room temperature.&apos; This phase is also a superconductor below about 3.4k9 The phase InSb(I1) is retained at atmospheric pressure if it is quenched to 78°K under pressure,6,7 but tends to transform at higher temperatures and does so explosively above approximately 210ok,7 A value of the heat of transformation of InSb(1) to InSb(II) at 210°K and atmospheric pressure has been reported.&apos; A concurrent publication&apos;0 reports evidence for a new solid phase InSb(III), which was formed by annealing InSb above 58 1°K at 37 kbar, above 560°K at 52 kbar, and above 473°K at 65 kbar. Specimens of InSb(II1) had a superconducting transition temperature of 4.lo ± 0.1oK. X-ray diffraction patterns also indicated the presence of a new phase. In this communication, thermodynamic properties of the phases InSb(I), InSb(II), and InSb(II1) are reported and discussed. The phase boundary InSb(I)/InSb(II) and the relative positions of the triple points are calculated. 1) EXPERIMENTAL 1.1) Preparation of Specimens. Specimens of the high-pressure phases of InSb were prepared in a belt-type high-pressure chamber by a tichnique described in detail elsewhere.&apos;&apos; Charges of 0.6 to 0.8 g of Cominco semiconductor grade InSb were used. The temperatures were measured with a chromel-alumel thermocouple, the hot junction of which was within 0.5 mm of the specimen. The specimens were heated under a pressure of 37 kbar for 1 hr at 723°K (which is well above the liquidus) and quenched to room temperature. One set was annealed at 523°K and another set at 623°K for 20 to 24 hr. These annealing temperatures were chosen because 523°K was below and 623°K was above the temperature of the transformation of InSb(II) to InSb(1Tl) at 37 kbar.10 The specimens were then cooled to 125°K by passing liquid nitrogen through the jacket of the belt die before the

Jan 1, 1968

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By N. A. Gokcen, J. Chipman

A revised treatment of the authors&apos; published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors&apos; found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K&apos;2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K&apos;3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur&apos;s data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.&apos; In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K&apos;1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K&apos;1 and the following average values are suggested both for K, and K&apos;, at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-&apos;. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,&apos; which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley&apos;s tables of high-temperature heat contents" and entropies and with Korber and Oelsen&apos;s&apos; heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen&apos; is an evolution of 28,500 cal per gram

Jan 1, 1954

By J. H. Palm

Experiments have shown12 that the formula -S = St - (St - Se&apos;)e ne [1] expresses very well the relation between the true stress S and the true form monotonic deformation of plastic metals in single tension and compression (Fig 1). St (asymptotic or final stress), Se&apos; (threshold stress) and ne (characteristic or specific strain) are constants, the significance of which immediately follows from Fig 1. Only at the initial stages of deformation the experimental curve runs below the theoretical curve. This may be due, at least partly, to the uneven stress distribution caused by the anisotropy of the crystals. It is now obvious that a similar formula H = Ht- (Ht- He)e ne&apos; [2] might be valid for the relation between the hardness and the strain. The hardness can be only a function of the strain and must therefore be independent on the hydrostatic tension present in the neck during straining. Hence, if Eq 2 is correct it will also represent the relation between hardness and strain in the middle section of the neck, the strain of which is generally assumed to be almost or fully homogeneous. For aluminum, copper, and several copper alloys it is indeed observed that Eq 2 agrees very well with the experimental Vickers hardness-strain relation from zero strain on up to the strain at fracture. Moreover nc&apos; is, for several metals fairly equal to nc- Hence H = C1 + C2S [3] C1 and C2 are constants during uniform uniaxial tension. Eq 3 was also obtained for copper by Voce.3 According to Hencky&apos;s theory4 the ratio of the Brinell or Vickers hardness and the yieldstress (expressed in kg per mm2) of a non-strainhardening metal is approximately equal to 2.8. If Eq 1, 2 and 3 are correct the ratio Ht/S, must accordingly be the same for all plastic metals and be equal to 2.8. It is now experimentally established that this ratio varies between 2.7 and 3.1 with a mean value of 2.9. Taking into account that Ht and especially St can be obtained only by extrapolation from the range of rather low strains, the agreement with the theory is very satisfactory. References 1. J. H. Palm: Appl. Sci. Res. Al (1948) 198. 2. E. Voce: Jnl. Inst. of Met. (1948) 74, II, 537. 3. E. Voce: Metal Treatment (1948) 15, 53. 4. H. Hencky: Zlsch. f. angew. Math. and Mech. (1923) 3, 241.

Jan 1, 1950

By A. J. Hatch

Recent disclosures concerning strengthening of anisotropic sheet materials under biaxial stresses are reviewed. This biaxial strengthening has been termed "texture hardening" by Backofen and is related to the normal anisotropy parameter, R. Measurements of R made on three annealed titanium alloys indicate a Ti-4Al alloy will have the greatest potential for texture hardening, followed in order by Ti-5Al-2.5Sn and Ti-6Al-4V. Relative to sheet texture, a review of the deformation mechanisms in titanium alloys would indicate that a preferred orientation for "texture hardening" is where the (0001) pole is normal to the sheet plane. This was confirmed by determination oj (0001) pole figures for the above three alloys. High R values are related to pole figures with (0001) normal to the sheet plane, whereas low R values are related to pole figures with (0001) split in the transverse direction from the sheet normal. PUBLISHED work by Backofen et al. 1 and Hosford and Backofen2 based on hill&apos;s&apos; mathematical theory of yielding in anisotropic metals has indicated that significant strength advantages under biaxial stresses are possible in hcp alloys, provided an ideal (0001) [1010] sheet texture exists. This tendency to strengthen under biaxial stresses has been termed "texture hardening".1 It can be quantita- tively characterized by a strain-ratio parameter, R, where R may be determined from the ratio of natural width strain to natural thickness strain as measured on a uniaxial test specimen cut parallel to the rolling direction. If R is greater than 1.0, then strengthening under biaxial tension would be predicted. Considering the a titanium alloys which have an hcp crystal structure, Williams and Eppelsheimer4 have reported that commercial-purity grades deviate from the ideal (0001) sheet texture mainly in an approximate 30-deg rotation of the basal plane, toward the transverse sheet direction. However, McHargue et a1.5 have shown that the angle of rotation of the basal plane is sensitive to alloy content. In particular, a titanium alloy with 3.8 pct Al was reported to have the ideal (0001) [1010] texture after cold rolling. Additionally, Backofen et a1.1 using plane-strain compression tests have reported R values greater than 5.0 for the commercial 0 alloy Ti-5A1-2.Sn (110-AT). In view of these findings, a program was initiated to further determine the potential of commercial Ti-5A1-2.5Sn and an experimental Ti-4A1 alloy with respect to "texture hardening". Also, because of its wide commercial use, Ti-6A1-4V was included in the investigation. BIAXIAL-STRESS THEORY FOR ANISOTROPIC MATERIALS Backofen ef al.,1 based on the mathematical theory of Hi11,3 has introduced the concept of "texture hardening". In this work, it was shown that possi-

Jan 1, 1965

By Walter E. Lewis

Myriad problems face all of us in the next decade. Vietnam, poverty, and pollution are perhaps the most pres- sing. A lesser one but still vital to us as a Nation is the slow hut apparently relentless extinction of the mining, metallurgical. geological and petroleum engineer. Are we doomed to take our place in the crossword puzzle with the moa. to be defined like it as an "extinct bird"? Or can we reverse the trend perhaps, in the next decade? The plain fact is we are an endangered species, and must resign ourselves to virtual extinction in the 1970&apos;s unless the trend is reversed. Probably, many of us have felt the problem will solve itself if left in the in-basket long enough, believing, that the trend will reverse solely on the basis of demand for these disciplines. This approach has not worked up to now, it gives no promise of working in the future, and furthermore, the problem has been in the in-basket much too long. The point is simply this: What can each of us do as an individual, or as part of a company, a State agency, a Federal agency, a university, or an organization such as AIME?

Jan 1, 1970

By M. S. NORTH

IT may be a far cry from the days of the old horse whim, and it is relatively a long way back to hand production in factories. Modern machinery has made possible deep shaft-sinking, newer methods have increased the recovery of mineral. Technically, excavating and ore dressing have advanced as has mass production and its many ramifications in the manufacture of commercial product. To those of the mining industry who would have us believe that mining and manufacturing are totally different enterprises, it can be said that certain differences do exist. These differences rather than being fundamental are the result of adhering to past practices which were possibly sound years ago but do not measure up today. Differences in managerial control, sales, and distribution, cost finding, etc., are often so pronounced that efforts to compare or contrast are almost futile.

Jan 1, 1930

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.&apos; However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By Francisco Cadena

THE construction of Norris Dam, built by the Tennessee Valley Authority on the Clinch River, a tributary of the Tennessee River, involved the production of coarse and fine aggregate for approximately 1,000,000 cu. yd. of concrete. A hammer-mill plant for the manufacture of sand from quarried rock was indicated as the most economical method of providing this material. The abrasive character of the feed as compared to the average hammer-mill feed made it necessary to control operations rather closely, and this resulted in the accumulation of many data bearing on production and maintenance. This paper will deal only with three specific sets of data, accompanied by such general information as may be necessary to explain the conditions under which they were obtained and followed by discussions on the relation of silica content to hammer wear, comparative costs of slugger and stirrup hammers, and comparative costs of tool-steel and manganese-steel grate bars. Coarse Aggregate Aggregate for the concrete poured at Norris Dam came from a dolomite quarry within 2000 ft. of the west abutment of the dam. Geologically this rock is known as a Knox dolomite. A typical chemical analysis is given in Table 1. TABLE 1 .-Typica.1 Chemica1 Analysis [PER CENT H20,1100F ............................................ 0.0&apos;2 Ignitionloss ............................................. 43.56 MgO .................................................. 19.19 CaO .................................................... 29.07 FezO .................................................... 0.39 A1203 .................................................... 1.94 FezO .................................................... 0.39 A1203 .................................................... 1.94 ..................................................... 5.75 SO2.. .................................................. Tr.] Rock was carried by 12-yd. dump trucks to a 42-in. gyratory crusher set at 6 1/2 in. The product of the primary crusher was taken by a belt conveyor to a double-deck vibrating screen followed by a 5 1/2-ft. cone

Jan 1, 1937

By P. Niessen, S. J. Bercovici

RECENTLY Aust et al.&apos; proposed a model of non-equilibrium grain boundary segregation based on a vacancy gradient induced uphill diffusion process of solute to grain boundaries. According to their proposal, solute atoms which are attracted to vacancies would, during the cooling of a sample, migrate with vacancies toward grain boundaries (vacancy sinks) and thereby enhance the solute concentration in boundary regions. For solute atoms which are not attracted to vacancies no such boundary solute enrichment would be expected. These concepts were given experimental support by boundary and bulk mi-crohardness measurements of various thermally treated dilute zinc and lead alloys and also doped aluminum oxide. The underlying assumption in their work was that solute enrichment in boundary regions is indicated by higher microhardness values. From thermodynamic considerations1&apos;2 it appears that the solid-liquid solute distribution coefficient (K), defined as the concentration of solute in the solid to the concentration of solute in the liquid at equilibrium, indicates whether attractive or repulsive forces exist between vacancies and solute atoms. K < 1 indicates a solute-vacancy attractions, K > 1 indicates no, or a repulsive, vacancy-solute interaction. This note is to report on observations of different grain boundary etching phenomena in high purity zinc alloys. These phenomena appear to depend on whether a K < 1 or K > 1 solute is present. In experiments designed to measure directly the solute enrichment in grain boundary regions, samples of zone refined zinc with 0.1 at. pct solute additions were cooled from 380°C at a rate of 3°C per min. A surface layer of approximately 50 was then removed from the samples by chemical polishing. The samples&apos; surfaces were then protected by a chromating treatment such that in a subsequent etch only grain boundary regions were dissolved. The dissolved regions were approximately semicircular troughs, 10 µ in width. The grain boundaries were usually in the middle, i.e., at the bottom, of this trough. For zinc containing the K < 1 solutes cadmium and aluminum, the grain boundary was always indicated by a ridge as shown in Fig. 1. For pure zinc, and zinc containing the K > 1 solutes copper and gold, a groove at the bottom of the trough indicated the boundary position, Fig. 2., To test if these different grain boundary etching behaviors were possibly connected with the segregation process discussed above, the Zn-Cd alloy was again heated to 380°C and quenched into brine. After surface protection and etching it was found that this specimen no longer exhibited the grain boundary ridges but rather grain boundary grooves as shown in Fig. 2. It would appear, therefore, that the boundary ridge is a consequence of a process occurring during the slow cooling of the samples. From absorption spectrophotometric analysis it was found that for slowly cooled samples containing K < 1 solutes, the solute/zinc ratios of the material from the boundary trough were consistently considerably higher than the solute/zinc ratios of the bulk alloys. This boundary region solute enrichment was not observed in quenched samples. It is concluded therefore, that the boundary ridge shown in Fig. 1 is directly or indirectly connected with nonequilibrium solute segregation.

Jan 1, 1970