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By J. M. Seeman, R. A. Dodd

If some solution-quenched supersaturated aluminum solid solutions, e.g.., Al(Cu), are plastically deformed at room temperature and then aged at 200oC, the hardness may first decrease before increasing in the usual manner ' A similar transient softening is observed, even in the absence of plastic deformation, when a thin foil or small-diameter wire Al(Cu) specimen is rapidly quenched from the solution-treatment temperature and then aged.' Also, some solution-quenched and neutron-irradiated alloys undergo an initial hardness decrease during subsequent aging.3 The usual explanation of the transient softening in the above examples involves the effect of vacancies introduced by plastic deformation, rapid quenching, and neutron irradiation, respectively However, the mechanism of softening is not unequivo-cably established. In the first-noted case, Gane and parkins' observed that the softening was approximately proportional to the difference in the atomic diameters of solute and solvent, and it was argued that, if a large relative difference in atomic diameter promoted vacancy-assisted room-temperature solute diffusion to dislocations, dislocation climb occurring during subsequent aging at 200°C could cause transient softening. Some substantiation of this theory was offered by the additional observation that discontinuous yielding of solution-quenched polycrystalline Al(Cu) tensile specimens was suppressed by interrupting the test for a short aging treatment at 200°C. Of course, reversion (resolution of GPI) at 200°C would also cause softening, and Sil-cock4 expressed the opinion that the softening in the case of Al(Cu) must be partly associated with reversion. Also, Hirsch5 commented on the possibility that, if jogs cause hardening, an anneal at 200°C should straighten the jogged dislocations and result in softening. However, parkins' has re-expressed his belief that these mechanisms are not entirely consistent with the observed serrated stress-strain curves. Experimental. New data has now been obtained for Al(Cu), Al(Ge), Al(Mg), and Al(Zn) primary solid-solution alloys. These alloys were prepared from metals exceeding 99.99 pct purity, and specimens 4 by 4 in. diam were solution-treated, quenched, deformed 10 pct in compression at room temperature, and aged at 200'C in a cottonseed oil bath for various times. Generally, these operations could not be carried out in rapid succession, so the alloys were stored in a freezer between treatments to minimize aging. The variation in hardness with aging time, Figs. 1 to 4, was determined by microhardness testing with a 3.0-kg load. At least five readings were averaged to obtain each data point, and all measurements were taken about the center circumference of each cylinder (region of maximum deformation). Each specimen was used to obtain only one data point, i.e., specimens were not replaced in the aging bath after measurements were made. In

Jan 1, 1968

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.' A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.' Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968

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

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

Jan 1, 1968

By John W. Cahn

Tile avevage value of the mean curvature of surfaces in a specimen can be precisely delermined by sitrlple measurements performed on random sections or on 1 vojectiotzs of these surfaces. For surjaces enclosing particles, the quanlity is sllown to be velated to the probable tlurrrhev ot particles intevcepted by a random platne and, under certain conditions, to the perimeter of their Projected image and to the increuse in surjace area when the particles grow. Many of the velalionsl~ips are valid for any shape or size of the particles. THE recent growth of the field of stereology or quantitative microscopy is largely the result of the discovery of a limited number of rigorously defined geometrical parameters that can be precisely measured on random sections or projections of a structure without assumption about particle shape.' Such parameters have been the volume fraction and surface area and line length in a unit volume. The present paper introduces the average of the mean curvature of surfaces in a volume, and shows that it can be rigorously measured by counting methods alone. AVERAGE CURVATURE ON A PLANE Consider a curve y = v (x) on the xy plane. The curvature Kp in the plane at any point is given by Kp = (dZy/dx2)/[1 + (dy/dx)2]3/2. The average curvature along the curve may be defined as Kp = (1/L) fKpdl |1] where dl = [(dx)' + {dy)2]1/2 is the length of an element of the curve and .(dl = L is the total length of the curve. The integral on the right-hand side of Eq. [l] will be called the total curvature, It is dimensionless and readily evaluated by substituting d = arctan (dy/dx) to give ah which is the change in direction of the tangents to the ends of the curve, Fig. 1. Hence, Kp = (1/L)(?h) [2] It can also be seen that Eq. [2] is applicable in the limit of sharp corners. Even though the curvature is infinite at a corner, f Kpdl remains integrable and equal to the change of angle. The signs of the quantities Kp and dl are arbitrary and, if the areas adjoining the curve are equivalent, there seems to be no compelling reason to fix the signs. For a closed curve, however, it becomes worthwhile to use the signs to distinguish among different types of areas or phases enclosed. For such a closed curve AO = t2r and As a convention, we shall take the direction of the integration along the curve in such a way that the area or phase under consideration (henceforth called a) is kept to the left side of the curve, Fig. 1. Then Kp is positive where the curve is concave and negative where the curve is convex. For a closed curve Ad - +2n if the curve encloses a, and Ad = —2n if the curve is surrounded by a. PLANAR SECTIONS OF THREE-DIMENSIONAL STRUCTURE OF ISOLATED a PARTICLES Consider next a planar section of a microstructure containing particles of a in a matrix. We place no restriction on shape of connectedness of these particles, and begin by considering the curvature of only the boundary between a particles and matrix' Clumps of contiguous a particles are then treated as a single a particle. The two-dimensional section will show in a unit area na simple closed curves enclosing a particles and nh closed curves of holes, in-

Jan 1, 1968

By A. G. Preban, R. J. De Angelis, J. B. Cohen, P. Gordon, D. C. Brillhart

Changes in stored energy, resistivity, density, X-ray line broadening, and dislocation arrangements (from transmission electron microscopy) have been mensured on copper specimens shock-loaded at 75 to 435 kbars. The stored energy in shock-loaded copper and changes in density and resistivity are larger than those after conventional deformation. A high density of twins makes an appreciable contribution to all the measured quantities. Dislocation densities rise to values of 1011 lines per sq cm at the highest pressure. The resistivity, density, and X-ray In a study of the effects of shock loading on copper, changes in stored energy, resistivity, density, hardness, lattice parameter, line broadening, and dislocation structure have been examined after subsequent annealing of specimens shocked to various pressures. This paper presents certain aspects of the data, taken by two groups, one at the Illinois Institute of Technology, and the other at Northwestern University, and compares the changes in these properties, and what they indicate about the effects of shock deformation. measurements yield dislocation densities in substantial agreement at all pressures, after correcting for the effects due to the twins. At the higher pressures, electron microscopy yields dislocation densities that are lower by a factor of about 5 to 10. Dislocation densities from stored -energy measurements are high; this finding can be rationalized by the consideration that the deformation twin boundaries present are largely incoherent. There is no evidence for homogeneous dislocation nucleation during shock loading. Shock loading any metal or alloy, such as copper, causes a large increase in yield strength, with dimensional changes of the order of only a few percent."' Other properties have not been extensively studied, but this result clearly indicates the importance of examining the substructure. Previous studies of the substructure of conventionally deformed specimens have been made using electron microscopy,3-6 X-ray diffraction,7,8 and etch pitting.9,10 The dislocation density can reach values of about 10" per sq cm; and the dislocations are arranged in cells approximately 0.15 in size. The substructure varies widely, however, from point to point in the specimen. The substructure of explosively loaded copper consists of cells of about the same dimensions6,11 but their size is more uniform.6 Profuse twinning occurs12,13 and the twins are often too small to be detected optically.6,13 The boundaries outlining these twins appear to be incoherent.14 There is now ample evidence 13-15 that twinning is a strengthening mechanism in fcc metals but this is only part of the strengthening effect in shock-loaded copper.* From the twinning systems which operate in shock-loaded single crystals,13 and from changes in texture on shock loading,17 it has been shown that both the

Jan 1, 1968

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By S. Floreen, H. W. Hayden

The effects of additions of iridium, rhodium, ruthenium, and platinum on the mechanical properties of Fe-C alloys were determined. Each alloying element significantly improved the toughness. The results support the general correlation that substitutional alloying elements that stabilize austenite are beneficial to toughness, but the reason for this improvement is not obvious at this time. The effects of substitutional alloying elements on the toughness of steel has long been a subject of both practical and theoretical interest. Despite the obvious importance of this subject, there has been little progress toward understanding the mechanisms by which alloying elements influence the fracture behavior. In some cases the deleterious effects of alloying elements have been shown to be due to mechanisms such as embrit-tlement of prior austenite grain boundaries or inhibition of cross slip in the ferrite lattice. In other cases, however, the reasons for the change in properties are not clear. This is particularly true for elements, such as nickel, that improve the resistance to brittle fracture. Several investigators'-3 have pointed out that there is a correlation between an alloying element's phase diagram with iron and its effect on toughness. Those substitutional alloying elements that stabilize austenite generally are beneficial to toughness, while ferrite-stabilizing elements generally are detrimental to toughness. The word "generally" should be emphasized, because exceptions to this rule can be found. Nevertheless, this correlation does offer a starting point at which to try to understand the effects of alloying elements on toughness. Thus far only two austenite-stabilizing elements, manganese and nickel, have been considered. In order to test the validity of this correlation several other austenite-stabilizing elements were evaluated. The noble metals, iridium, rhodium, ruthenium, and platinum, have binary phase diagrams with iron similar to the Fe-Ni and Fe-Mn diagrams. That is, each element expands the austenite field, and also higher concentrations of each element produce martensitic transformations at low temperatures. Presumably then, each of these elements should improve the toughness of steel. The present study was conducted to determine if this were so. EXPERIMENTAL PROCEDURE The alloys were made as l-lb air-induction melts using electrolytic iron and commercially pure noble metals. Each heat was initially deoxidized by a carbon boil, and further carbon was added to attempt to produce a 0.05 wt pct C content in each alloy. Before pouring, a final refining addition of 0.2 wt pct A1 and 0.1 wt pct Ti was made to each heat. The alloys were cast in a copper mold to produce ingots approximately 1 in. in diam and 5 in. long. The chemical compositions of the alloys tested are given in Table I. The residual nitrogen, aluminum, and titanium contents were all relatively constant at 0.003, 0.03, and 0.02 pct, respectively. The carbon

Jan 1, 1968

By Kenneth K. Humphreys, F. R. Zachar, A. G. Gilbert

INTRODUCTION by F. R. ZACHAR and A. G. GILBERT Coal producers are not only faced with the problems of mining coal, but must also decide to what extent they can invest capital and what operating and maintenance expense they can afford, after mining, to market their product in sufficient volume and at a reasonable profit. Regardless of whether the operator is contemplating a new operation or merely considering expanding present facilities, market requirements, ability to make a product meeting requirements, probable costs and possible future changes in raw coal or finished product must be considered. In addition, such items as flow sheet, structural designs, storage facilities, etc, must be examined individually and collectively. In estimating preparation costs to meet predetermined market specifications, the operator must calculate the economics of present preparation practices to anticipate the increase to total production which results when the quality of the finished product is increased. The consumers of coal are continually seeking to obtain the best and most adaptable product for their money. Regardless of whether coal is used for coking, industrial requirements, electric power generation, domestic fuel or for other purposes, it will be scrutinized from such standpoints as delivered cost, suitability for utilization in certain equipment, ease of ash disposal, adaptability to material handling system plans and its potential for generating dust problems. Utilities, due to large capacity volume requirements, are generally in a position to select coal that will result in the lowest over-all cost per million Btu. Freight costs, paid by the utility, are important and are given utmost consideration when a coal is under consideration. Steel companies, whether producing or purchasing coking coal, are continually seeking coal that will result in lowering the cost of pig iron production. Since it is usually necessary to clean to lower specific gravities, say 1.40, to turn out a product meeting metallurgical requirements, it follows that a high ash "middling" product is created. These low quality middlings do not command a good price. Therefore, unless the metallurgical coal can command sufficient realization to carry or subsidize the middlings, the operator may be ahead economically to prepare steam coal at a higher specific gravity. While the "unit-train" rate reductions have been helpful to the economy of the coal industry, the establishment of these rates has made mandatory the installation of storage and rapid car loading facilities at mines and plants shipping utility coal (see Chapter 15). A study of the economics

Jan 1, 1968

By A. L. Slaughter

The Homestake mine, located in western South Dakota, was discovered in 1876. The first reported production was in I 878. Total production through 1965 is 6,554,249 troy ounces of silver and 27,961,276 troy ounces of gold, worth $987,000,000 at present prices. Precambrian sedimentary formations at Lead total 20,000 feet. The Poorman Formation, the oldest, is chiefly ankerite carbonate. The Homestake Formation is iron-magnesium carbonate. The younger formations are argillaceous with some quartzites. The Cambrian Deadwood Formation unconformably overlies the Precambrian. All are cut by Tertiary intrusives. Sideroplesite schist of the Homestake Formation was converted to cummingtonite schist in the zones of higher-grade metamorphism. The Precambrian rocks show the effects of extreme isoclinal folding. A second stage of folding ( cross folds) may have been caused by the Tertiary intrusives. All folds plunge to the southeast. The Homestake ore bodies are pipe-like replacements of the Homestake Formation in zones of cross folding. It is believed that dilatation of the schists has increased permeability in these zones. Chloritization of the schists is the most widespread effect of the mineralization which is divided into four stages. Principal minerals of the first stage are quartz, chlorite, and arsenopyrite; in the second stage, quartz, ankerite, and pyrrhotite. In the third stage only pyrrhotite was deposited. The fourth stage followed the intrusions of Tertiary dikes and deposited mostly pyrite and calcite. Gold accompanies all stages and is always the last mineral to be deposited. It is most closely associated with arsenopyrite of the first stage but can be interpreted as having been deposited during the fourth stage and superimposed on the products of the earlier stages.

Jan 1, 1968

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß&apos;) does not change significantly between 322o and 8000 K, confirming that the ß&apos; alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp&apos;s law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß&apos;) has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß&apos;) were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By Richard W. Brummett, Robert L. Dubms

Located some 180 miles east of Los Angeles in Riverside County, California, the Eagle Mountain mine supplies iron ore concentrates for the Kaiser Steel Corporation steel plant in Fontana, California, and for export to Japan. Although the deposits were first discovered in the early 1890's, no production was realized from the area until 1948 when Kaiser Steel Corporation commenced operations. A part of the large Basin and Range province, the Eagle Mountain area's geologic column comprises a thick series of metasediments resting on Precambrian gneisses and schists that have been intruded by sill-like masses of porphyritic quartz monzonite. The metasediments are composed of three quartzite units that are separated by a schistose meta-arkose and by two ore zones. They have been folded into a large east-west trending anticlinal structure that extends completely across the Eagle Mountains. The iron ore deposits occur in two well-defined horizons in the metasedimentary series, and they are found only along the north limb of the major anticline. Host rocks for the ore zones were a series of limestones and dolomites with associated quartzites. Magnetite plus pyrite comprised the primary mineralization that formed many replacement lenses and stringers of ore within the ore zones. The primary ore has been oxidized to hematite and goethite in a broad zone at higher elevations in the deposits. Hydrothermal alteration formed actinolite- tremolite granofels, local phlogopite, and minor tourmaline in the ore zones. This alteration and the ore deposition seem related to the same magmatic event that formed the porphyritic quartz monzonite intrusion

Jan 1, 1968

By R. A. Burmeister, P. E. Greene

Two methods for the synthesis and growth of single crystals of B6 P are described: a solution-growth process employing nickel as the solvent, and a vapor-growth process employing BBr3 and pH3 as the reac-tants. Relevant portions of the Ni-B-P phase diagram have been examined and liquidus data are presented for an isobaric section at an equivalent P2 pressure of 3.8 Torr, and an isothertnal section at 1300°C. Solution-growth techniques are described and the purity and crystalline perfection of the resulting material is discussed. Epitaxial growth of BeP on &P substrates has been obtained using the vapor-phase system. Evidence is presented which supports the assignment of the stoichioknetry B6P to boron sub-plwsphide. THE B-P system differs from other III-V systems in that it contains two distinct compounds. The existence of the monophosphide (BP) has been known for some time,&apos; whereas the subphosphide (B6P) was reported only recently.&apos; Both of these compounds are large bandgap semiconductors (Eg = 2.0 ev for BP~ and 3.3 ev for B6P4), and are therefore of interest for optoelectronic applications. The crystal structure of B6P is quite different from those of most semiconductors, being derived from that of a-rhombohedral boron by the incorporation of the two phosphorus atoms in the intericosahedral sites of the a-boron unit cell?76 B6P also exhibits a number of unusual characteristics, including a high degree of chemical inertness, hardness, and high-temperature stability. No information concerning other physical properties is available in the literature. The present study is part of a broader investigation of the preparation and properties of B6P. This paper considers methods of growing single crystals of B6P of suitable size and quality for physical-property measurements. A detailed discussion of the electrical and optical properties of B6P will be given elsewhere.&apos; GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP&apos; according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .&apos;" It is therefore possible, in principle, to apply several of the reactions reported for the synthesis of BP to the synthesis of B6P merely by selecting lower phosphorus pressures or higher temperatures, in accordance with the equilibrium data. Other techniques for the direct synthesis of microcry stalline B8P have also been reported.1°

Jan 1, 1968

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.&apos;&apos;&apos; Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~&apos;~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace&apos; conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace&apos; and ~aeland&apos; have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-&apos; Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By M. C. Flemings, G. E. Nereo

General expressions are given to describe macro-segregation in castings and ingots which results from mass flow of solute-rich liquid to feed solidification and thermal contractions. Analytical solutions are given for solidification with planar isotherms (unidirectional and bidirectional heat flow). These solutions describe inverse segregation and centerline segregation. Numerical examples are given for A1-4.5 pct Cu alloy. In 1540, Vannoccio Biringuccio published one of the first references to macrosegregation, describing the problem of exudation and inverse segregation in the manufacture of bronze gun barrels.&apos; Since then, a great many studies of macrosegregation have been reported. Recent work of particular engineering interest includes that of Marburg 2 and others:" on centerline segregation and other types of segregation in large steel ingots, and work of Adams,5 Scheil, 6 and Kirkaldy and youdelis7 on inverse segregation in nonferrous ingots. In most studies on this subject, the various types of macrosegregation have been treated as separate phenomena. For example, quite different mechanisms have been proposed for formation of centerline segregation, negative cone of segregation, inverse segregation, banding, and so forth. In this, and in several papers to follow, it is proposed that these as well as other types of macrosegregation result from the same basic mechanism and can be quantitatively described by the same basic equation. It has often been suggested that some types of segregation (such as centerline segregation and banding) occur as a result of buildup of solute at the tips of growing dendrites.2-4 ,8-10 As example, banding can be induced in centrifugal castings by mechanical vibration, and Northcott 10 suggests this might be due to the influence of the vibration on the boundary layer at the dendrite tips of the growing dendrites. However, in view of the extremely small boundary layer known to exist at the tips of the dendrites,11,12 any interpretation of macrosegregation based on this boundary layer is clearly incorrect. Note that experiment has shown that significant buildup of solute does not occur at dendrite tips in ingot solidification, but even if such buildup occurred the thickness of the enriched zone would only be the order of D/U where D is liquid diffusion coefficient and U is dendrite tip velocity. For usual casting or ingot solidification this solute-enriched layer is 10"3 cm, far too small to account, for example, for centerline segregation.11&apos;12 It has also been suggested that convection in the bulk liquid (ahead of the advancing dendrites) might cause segregation by sweeping away the solute-rich boundary layer in front of the dendrites.3 However, since there is no significant boundary layer, this explanation must be incorrect. The convection might directly cause segregation by penetrating between the dendrite arms, and presumably in a rimming steel ingot it is sufficiently vigorous to cause some segregation in this way. Centerline segregation, however, cannot be interpreted as resulting from this convection since a sharply segregated zone is usually found near the centerline, with the bulk of the ingot being nearly of nominal composition. If convection in the bulk liquid were the direct cause, a gradual change in ingot composition over the entire cross section would be expected. It is known that sudden changes in convection of the bulk liquid during solidification can result in banding,14 but it is not clear that the banding results directly from the effect of convection on solute distribution. Changes in convection also affect thermal conditions in the liquid-solid region of a solidifying ingot. It will be seen later in this paper, and in a paper to follow, that macrosegregation is strongly influenced by these thermal changes. Recognizing that in some cases of ingot solidification (as in solidification of rimming steels) convection in the bulk liquid may have a direct effect on solute distribution, we neglect it in this paper and in the several to follow. We then derive general expressions describing macrosegregation which results from the mechanism of interdendritic flow of solute-rich liquid

Jan 1, 1968

By David P. Shoemaker, Clara Brink Shoemaker

The I phase was discovered by Bardos, Malik, Spiegel, and Beck1 in the V-Ni-Si system at 1100°C and in the Mn-Co-Si and Mn-Ni-Si systems at 1000°C. Kuzma and Hladyshevskii2 and Kuzma, Hladyshevskii, and cherkashin3 have reported a new phase, which they named the S phase, in the Mn-Co-Si and the Mn-Ni-Si systems at 800°C at approximately the I phase compositions. The powder diffraction diagrams of the I and S phases, compared by Bardos el al.,1 are related but show distinct differences in relative intensities. Professor Paul A. Beck kindly sent us a specimen of the (v-Ni-Si) I phase for single-crystal study. Precession and Weissenberg diagrams taken with a tiny single-crystal fragment showed that the structure is monoclinic with a large unit cell. The cell dimensions were refined from a powder diffraction diagram taken with CrKa radiation in a 57.3-mm camera with our computer program LSCELP4 using only the indices of those reflections that were observed on Weissenberg diagrams (hnl, with n = 0 through 9 and n = 12) and precession diagrams (Okl, lkl, Izk0, hkl, hk2). Table I shows the agreement obtained between the l/d values calculated with the final values for the cell dimensions and the l/d values observed by Bardos et al .1 for I(V42Ni33Si25), by US for I(V41Ni36Si23), and by Kuzma and Hladyshevskii2 for S(MnpCoSi). The powder patterns contain many broad and diffuse lines. In fact practically all powder lines observed are near-superpositions of several reflections. The refinement program is not set up to handle several reflections contributing to one observed line: the position of each line is refined with the aid of one set of indices only. The final values for the cell dimensions were obtained from the lines of strong or medium intensity with the indices indicated by asterisks in Table I: a0 = 13.403(6), bo = 23.336(15), co = 9.129(6)A ß = 99.11(6) deg The standard deviations (given in parentheses) are those calculated by the refinement program from least-squares theory and do not take into account that the lines included in the refinement may not have been correctly indexed in every case or that the position of a line may also be partly determined by the overlapping reflections. The agreement between the calculated and observed I phase patterns is fairly good, although some discrepancies occur. Not all observed lines could be indexed with the incomplete set of sin-

Jan 1, 1968

By A. Hellawell

Specitlrens of the Al-Ge eutectic alloy have been frozen unidivectionally at rates between 2.5 x 10-6 and 2.5 x 10-4 cm per sec and the structure examined by optical and X-ray methods. There is no epitaxial relationship between phases, the aluminum having random orientation and the germanium a preferred (011) fiber textuve. Lamellar colonies which are BINARY eutectic alloys occur between either silicon or germanium with the metals aluminum or silver. common in this alloy are constructed from axial and nonaxial (111) plates of germanium which are related by a variety of twin configurations. Irregular or globular regions of the microstructure are composed of continuous single crystals of each phase, the germanium being heavily twinned. There is limited solid solubility in these systems, and the eutectic phases all involve diamond cubic with fcc crystal structures. In the microstructures of these eutectic mixtures the silicon and germanium crystals exhibit an almost infinite variety of shapes which are notably sensitive to

Jan 1, 1968

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a&apos; matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a&apos; plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.&apos; Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y&apos; alloys by gas quenching, is extensively ordered prior to y&apos; (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y&apos;, Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y&apos;. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y&apos;, or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.&apos; The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.&apos; An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968