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By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.' These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,' one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z' alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

By G. Sandoz, D. A. Meyn

The fracture surfaces of specimens of titanium a1loys which exhibited susceptibility to subcritical crack growth in a wide variety of environments, including aqueous solutions, alcohols, hydrocarbon gases, carbm tetrachloride, and dry air, were examined. The dominant and characteristic fracture mode was cleavage. which became mixed with an increasing porportion of ductile fracture modes (dimples. and so forth) as the applied KI was increased. The cleavage plane in all the alloys was oriented at 15 deg from (0001) of the a phase. No indices could be assigned to the 15 deg cleavage Plane because of uncertainty as to which zone it belonged to. SLOW crack growth and delayed fracture take place in certain titanium alloys at stress intensity (KI) lower than the critical values for complete fracture (KIc) found in short-time tests for plane strain fracture toughness.' Such crack growth may take place in very dry air on sustained loading if the alloy contains a sufficient amount of hydrogen and if the stress intensity factor is higher than a threshold value designated KIH.2 Similarly, a number of environments such as water, alcohols, and hydrocarbons may cause slow crack growth provided the stress intensity factor exceeds the threshold value KISCC. In this paper it is intended to examine some fracto-graphic and crystallographic details of this subcritical crack propagation process as related to alloy composition, environment, and stress intensity. It has been previously reported that subcritical crack growth takes place in titanium alloys in aqueous environments by cleavage.2"6 The observations to be described here indicate that in the alloys investigated the mode of subcritical crack propagation is more dependent on the stress intensity during cracking than on the environment. The fracture mode is illustrated with photographs of the fracture surfaces at a wide range of magnifications. The crystallographic character of the cleavage mode is also presented and the results discussed. EXPERIMENTAL APPROACH The studies were made on four titanium alloys— Ti-8A1-1Mo-lV, Ti-5A1-2.5Sn, Ti-7Al-1Mo-lV, and Ti-0.350. Of these four alloys the first two were mill annealed and fine grained. The latter two were noncommercial and coarse grained, having been prepared for other experimental purposes. The crystallographic studies required a large-grain size. Consequently the fine-grained alloys were an- nealed in a vacuum at 1950°F and furnace cooled to produce samples for these studies. This treatment did not alter the microstructure significantly except for grain size. All the aluminum-containing alloys showed primary a with a network of ß-phase particles within the a grains; Figs. 1 and 2 show this microstructure for the specific case of fine-grained Ti-8A1-1Mo-1V. The cracks in the figures will be discussed later. Fractographic studies were made on all the alloys, but the electron fractographs displayed herein are from the Ti-8A1-1Mo-1V alloy in the fine-grained condition. Emphasis was placed on this commercial alloy because considerable information was available on the stress-corrosion cracking characteristics in a variety of environments. Sufficient supplementary studies of the alloy after the anneal to produce large grains were conducted to establish that the stress-corrosion cracking susceptibility and fractographic characteristics were not changed significantly. Thus it could be inferred that the crystallographic data obtained exclusively on large-grained specimens would apply also to fine-grained specimens. Fracture surfaces for study were obtained using precracked cantilever beam specimens loaded as described by Brown. The precracked section of a specimen was immersed in the environment of interest. Values of initial stress intensity factor Kli were chosen slightly higher than KISCC in order to obtain a fairly extensive region of slow crack growth. Fracture surfaces representative of a variety of stress intensity levels could then be examined because in the cantilever beam test KI increases as the crack propagates.

Jan 1, 1970

By W. L. Mamme, G. Y. Chin

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain was analyzed by Taylor and by Bishop and Hill in terms of a minimum (internal) and a maximum (external) work criterion, respectively. These two criteria have now been generalized to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (noncrystallographic) pencil glide. The generalized treatment also takes into account the possibility of a Bauschinger effect and of unequal hardening among the shear systems, which were considered in the Bishop and Hill work. Optimization techniques of linear and nonlinear programming are shown to be applicable for the numerical calculation of the minimum or maximum work. In the case of crystallographic shear, the constraint functions are linear and hence the optimal work is obtained as the saddle value of the lagrangian function Wi(y) e minimum and W,(u) + (a) for the maximum, where Wi is the (internal) work, We is the (external) work, Y is the crystallographic shear strain, u is the applied stress, and and are constraints. It is shown that the Lagrangians are functionally the same and the saddle value of one problem is identical to the saddle value of the other, proving that the two analyses are completely equivalent. In the case of pencil glide, although the constraint functions are nonlinear and neither convex nor concave, the equivalence of the optimal values to the saddle value of the Lagrangian (which is again identical for both problems) is still valid. WHEN a crystal deforms plastically by crystallographic shear, five independent shears are generally required to accommodate five independent strain components specifying the deformation. Assuming slip as the only shear mechanism, Taylor1 in 1938 analyzed the deformation in terms of a minimum work criterion. He hypothesized that of all combinations of five slip systems which are capable of accommodating the deformation, the active combination is that one for which the internal work C is a minimum, where 1 TI is the critical resolved shear stress for slip on the 1-th slip system and is the corresponding simple shear. By further assuming equal 72 for all equivalent slip systems and no Bauschinger effect, Taylor re- duced the minimum work problem to one of minimum and applied the analysis to the case of axisym- Metric flow by {111}(110) slip in fcc crystals. However, he did not consider the question of whether the resolved shear stress has in fact attained the critical value for slip on the newly found active systems without exceeding it on the inactive systems. In 1951 Bishop and ill' put forth the maximum work analysis in which slip is again assumed as the only deformation mechanism. In this analysis, the work o1 done in a given strain ij by a stress ujj not violating the yield condition is maximized. In addition, the analysis takes into account the possibility that the critical resolved shear stress for slip may not be equal among the slip systems and that the slip behavior may exhibit the Bauschinger effect. As with Taylor, a single set of slip systems—{111)(110) — was analyzed numerically. It thus appears that the Bishop and Hill treatment is on a more sound physical basis than the Taylor treatment. However, Bishop and Hill showed that where there is equal hardening among all slip systems and when there is no Bauschinger effect, Eq. [11 ] of Ref. 2, as assumed by Taylor, the results of their maximum work analysis are the same as those of Taylor's minimum work analysis. Hence at least under those conditions there is an implication that the Taylor analysis does lead to a critical resolved shear stress for slip on the predicted active systems without violating the yield condition on the inactive systems. Recently, the Taylor analysis was applied for numerical solutions of the axisymmetric flow problem, for slip on {110}(111), {112}(111). {123)(111) systems as well as a mixture of all three sets of svstems."1 Computational techniques based on the optimization theories of linear and nonlinear programming4 were employed in these solutions. The same techniques were employed in the solutions of an axisymmetric flow problem of deformation by slip on (111) (110) systems and twinning on (111)(112) systems5 which had been considered theoretically from a modified Taylor approach. The utilization of these techniques has led to the realization that the solutions of Taylor's minimum work problem imply the solutions of Bishop and Hill's maximum work problem. The two problems turn out to be dual problems in the well known sense of mathematical programming. It is thus the purpose of this paper to first generalize the minimum and maximum work analyses to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (non-crystallographic) pencil glide, as well as the possibility of a Bauschinger effect and of unequal hardening

Jan 1, 1970

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By M. Marciano, K. Kreider

Silicon carbide coated boron fiber (Borsic) reinforced aluminum composites were made which exhibit strength and modulus values predicted by the rule of mixtures. A successful technique for fabricating these composites consists of plasma spraying of monolayer filament reinforced tapes and subsequent diffusion bonding of these tapes into composites. The elastic properties of the composites were given by the rule of mixtures in reinforced directions. (The modulus parallel to the fibers was 32 x 106 psi for a composite with 50 pct by volume fibers. The other elastic properties for a composite with 50 pct fiber were transverse modulus = 14 to 16 X 10 psi, G = 9.5 x 106psi, and v,, = 0.23. Tensile strengths of over 190,000 psi were measured for the composites with 50 pct fiber and the average strength for these composites was 162,000 psi. These same composites had interlaminar shear strengths of 12 to 15,000 psi. Multidirectionally reinforced composites demonstrated the same reinforcement efficiency in strength and modulus as the uni-directimlly reinforced composites. Comrpessive strengths of composites with 50 pct by volume fiber were found to be greater than 250,000 psi. STRUCTURAL filamentary composite materials are being considered for use where high strength, high modulus, and lightweight materials are required. Metal matrix composites have been considered for use at temperatures ranging from cryogenic (aluminum stainless steel) to 6000°F (plasma sprayed tungsten plus tungsten fiber) and other requirements have been similarly diverse. Metal matrix composites offer high modulus and high strength in unreinforced directions, the ability to be joined by brazing or welding, and greater fracture toughness compared with the more easily fabricated resin matrix composites. This paper deals with the mechanical properties of aluminum boron composites, a system which is being considered for applications where lightweight, high modulus, and high strength are required at temperatures including those above the normal operating temperatures of resin composites. The boron fiber used in this investigation had an average room temperature strength of greater than 400,000 psi, a modulus of 58 x 106 psi, and a density of 0.09 lb per cu in. (2.6 g per cu cm).' The fiber used in the composites had a coating of silicon carbide to retard degrading reactions with the matrix at elevated temperatures. The coated fiber, which is sold commercially as Borsic: has been reported to have excellent resistance to degradation at temperatures up to 600°C in air and in aluminum2 and the same mechanical properties as the standard bare boron fiber. Fabrication of Composites. The composites were diffusion bonded from plasma sprayed monolayer tapes. These tapes were fabricated on a substrate of aluminum alloy foil which is incorporated in the composite matrix. The technique consists of winding a layer of fiber on the foil, and plasma spraying the balance of the matrix alloy over the windings which bonds all of the components together. Advantages of this process include the ability to achieve good fiber spacing, Fig. 1, the formation of a good bond between fiber and matrix (achieved during the plasma spraying), and the adaptability of the process for forming large and complex parts. This is particularly true when used with brazing foil backing which alloys low pressure bonding of the structural shape. PROPERTY EVALUATION TECHNIQUES Tensile test specimens, 5 to 7 in. long with a reduced gage section and ,030 to ,040 in. thick, were cut from composite sheets with a diamond saw. The gage section was .200 in. wide, while the gripped section was .240 in. wide and over 2 in. long in each grip. The standard gage length used was 1 in., however, transverse specimens (i.e., specimens with the fibers oriented 90 deg to the loading axis) were tested without a reduced section. Twelve specimens were also made with a 3-in. gage length but no significant effect of gage length was measured. The tensile test specimens were mounted in a fixture and aligned in friction grips using a 10X microscope. Unbonded foil doublers (0.010-in.-thick aluminum) were used to insure firm gripping with a minimum of damage to the fibers. The test specimens were transferred to the testing machine in a rigid fixture and mounted in the self aligning loading train. Testing was performed using a Tinius Olsen four screw testing machine with a torsion bar LVDT load

Jan 1, 1970

By B. J. Shaw, R. Kossowsky, W. C. Johnston

High purity (99,95) Ni-51 wt pct cr eutectic alloy was unidirectionalty solidified at rates of 0.1 to 8 in. per hr. The resulting material was characterized by large grains, approximately 0.5 mm in cross section and extending through almost the entire length of the specimen, parallel to the growth axis. The eutectic structure of specimens the growth at -1/3 The per hr consisted of a continuous nickel-rich phase and chrome -rich lamellae approximately 2 thick, spaced about apart. Specimens were tested in compression at temperatures ranging from —196 to 850"C over which range the 0.2 pet yield strength dp -creased from 160,000 p si to 35,000psi, respectively. Swaging to 40 pet reduction in area, followed by a 30-min anneal at 1000c to remove residual cold work, increased the 0.2 pet yield to 260,000 psi at -196°C, dropping to 35,000 psi at 850°C. The increase in strength was attributed to a residual cell structure. The strength of the alloy could be rationalized by the simple rule of mixtures if one assumed that additional strength is derived front a size effect characterized by is petch equation IN recent years there has been increasing interest in dispersion and second phase strengthening in materials needed for high-temperature applications. inm role of structure on the mechanical The of such alloys has been well established of such some extent accounted for theoretically. and to of how the strengthening mechanisms due to fibers and lamellae operate has been reduced to its fibers form by the fabrication of composites of strong rods unidirectionally aligned in a From work on tungsten-fiber-reinforced copper, for example, it was established that the "Rule of Mixtures" could explain the strengthening.12 " some what more sophisticated technique for introducing strong fibers into copper matrix was used by Hertzberg strong Kraft3 who unidirectionally solidified the copper-chromium eutectic. The use of unidirectionally fied eutectics has advantages in that there are no matrix-fiber wetting problems and fine fibers are automatically aligned and uniformly fiber However, one Is restricted to a specific volume fraction of the second phase. Nevertheless, even though the volume fraction is fixed, the rod or lamella thickness, , can be varied by controlling the freezing interface velocity. Alternatively, the grown material may be worked down by swaging or rolling. Embury and Fisher, " using this approach, drew down pear lite in iron and studied the mechanical properties iron and that the yield strength, oy, was properties.proportional They that d was the wire diameter. It could be inferred that was also proportional to but the work hardening had to be taken into consideration at the same time. By varying the growth rate of the cadmium-zinc lamellar eutectic, Shaw'1 showed that was proportional to without the introduction of work hardening and suggested that the lamellar interface itself contributed to the strengthening of the composite. In this investigation we have evaluated the mechanical properties of the unidirectionally solidified fec-bec eutectic Ni-Cr. This eutectic was selected because it presented the possibility was selected beca temperature, and high corrosion resistant alloy, and also represented a hard-soft phase combination with two completely different slip systems. Specimens were tested in compression and tension up to 850°C and a detailed study of the micro structure as a function of plastic strain and temperature was carried out by light and electron microscopy. It was shown that the composite strength tested in compression can be accounted for by the simple rule of mixtures if one allows for an additional term representing the effect of Intereprese EXPERIMENTAL PROCEDURE 1) Unidirectional Solidification. Fig. 1 is a schematic drawing of the apparatus used to produce 0.2 in. diam by 12 in. long alloy ingots. The crucible tube is alumina, containing the charge which has been is swaged, or machined to 0.195 in. diam. The lower end of the tube is immersed to 0 .195in in.d iam. The upper end is supported by a 10 mil nichrome wire which lowers the crucible mil nic hr the] wire at a prescribed rate. Surrounding the furnace is a graphite susceptor into which a control thermocouple is inserted. The furnace is insulated with fiberfrax and enclosed in a quartz tube. There is a sliding seal at the bottom around the crucible and one on the top so that an atmosphere may be used for the sample and suscep tor. The power for the furnace is supplied from a 10-kw, 450 kc generator. The skin depth (the skin depth at which the field falls to l/e of its value at the outer surface) for graphite (p = 10 (j-ohm-cm) is 0.1 in. at this fre-

Jan 1, 1970

By W. R. Kanne, P. R. Strutt, R. A. Dodd

A study has been made of the creep behavior of ß-NiAl of stoichiometric composition in the temperature range 475" to 775°C. Single crystal tensile specimens were deformed under a constant applied load. From slip line studies and tensile axis rotations it was concluded that the crystals deformed by pencil-glide on (100) and (110) planes with a (100) slip direction. Electron microscope thin-film studies showed evidence for profuse cross-slip, and the dislocation Burgers vector was determined to be (100). There was no tendency for the dislocations to lie in definite slip planes, although a strong alignment of segments of edge dislocations was frequently seen. The activation energy for creep in the temperature range 475" and 775°C was judged to be much lower than that for creep at temperatures above 775°C. It is possible that the rate-controlling process is the thermally activated cross-slip of screw dislocations. In recent years considerable interest has developed in the possible use of high-melting-point intermediate phases for high-temperature applications necessitating good creep resistance. Ordered alloys such as Ni3A1, modified by alloying additions, have received particular attention, culminating in the recent development by Pratt and Whitney of single crystal turbine blades.' The intermediate phase NiAl has considerable theoretical interest from a creep standpoint because not only is it ordered up to the melting point (-1650°C at stoichiometry) but it contains a high concentration of structural vacancies on the aluminum-rich side of stoichiometry. These vacancies are known to exert a strengthening effect under some conditions,' but in addition they might be expected to affect high-temperature creep rates through dislocation climb. The present paper deals with the slip line and dislocation structures developed during creep of stoichiometric NiAl between 475" and 775C, and with possible attendant creep mechanisms. MATERIALS AND TEST TECHNIQUES NiAl ingots of stoichiometric composition were prepared by induction melting 99.996 pct A1 and 99.98 pct Ni (kindly provided by the Kaiser Aluminum Co. and the International Nickel Co., respectively) in 100 cc pure alumina crucibles in a helium atmosphere. No chemical melting flux was used in order to avoid con- tamination of the alloy. Each ingot was slowly direc-tionally solidified to avoid porosity and to produce very large grains up to 2 in. in length. In this way, ingots were obtained which were suitable for sectioning into single crystal creep specimens. Chemical analysis indicated that all alloys were within the range 49.6 0.3 at. pct Ni. For the present investigation, identical rectangular single crystal blanks were cut vertically from one particularly large crystal in an ingot using a series of three diamond cut-off wheels with appropriate spacers. Thus, all sliced crystals had the same orientation with the tensile axis parallel to the long side of the rectangle; the initial orientation of the tensile axis is shown as S, in Fig. 1. The blanks were homogenized at 1250 to 1300°C for 48 hr and subsequently cooled slowly to room temperature. A gage length of rectangular cross section and about 0.75 in. in length was prepared on each specimen using an electrolytic lathe and a dilute nitric/phosphoric acid electrolyte. The gage length cross section was 0.250 0.0005 in. by 0.040 ± 0.0005 in. Holes to accommodate tensile grips were electrolytically machined using a rotating acid jet. After creep testing, this same technique was used to cut discs for transmission electron microscopy. Thus, all shaping was done electrolytically, the only exception being that (122) sections were spark-machined from some speci-

Jan 1, 1970

By R. Wang, N. J. Grant, B. C. Giessen

By crystallographic and X-ray methods, the existence and isonzorphism of Ti3Rh5 and Hf3Rhs were confirmed. Both phases are of the orthorhombic Ge3Rh5 type; lattice parameters and refined positional parameters are given. The structure is related both to the filled-up NiAs-B8 and Cu-AI types. An analogous phase with zirconium does not exist; the effect of ternary substitutions for titanium ad hafnium suggests a size factor limit to be active. A recent survey of phase diagrams of the T4 metals titanium, zirconium, and hafnium with the T, noble metals rhodium and iridium indicated the existence of the A3B5 phases Ti3Rhs, ZrsRhs, and HfsRhs. Ti3Rhs and Hf3Rh5 were found to be isostructural, based on the line-rich powder patterns which had not been analyzed. Zr3Rh5 was considered to have a substructure of the NbRu type (orthorhombically distorted B2-CsCl type).&apos; Because, in combinations with other transition metals, hafnium and zirconium are generally more likely to form isostructural phases than hafnium and titanium (with the significant exception of the Ti2Ni-"E93" type phases based on T4 metals2), the reversal of this relation for the A3B5 phases was of interest. As shown in the following, the nonexistence of Zr3Rhs has been established, the structures of Ti3Rh5 and Hf3Rh5 have been worked out, and crystal chemical relationships and stability criteria are reported. EXPERIMENTAL METHODS AND RESULTS Alloy Preparation and Phase Diagram Work. Alloys were prepared from high-purity (99.99+ pct) elements by arc-meltin3,4.Heat-treated alloys were annealed in a vacuum of 3 x X torr for 24 hr at 1300DC. Metal-lographic samples were etched electrolytically in concentrated HCl with 5 v ac for 5 min.3 X-ray diffraction powder patterns were taken on a GE XRD-5 dif-fractometer with Cum radiation at low scanning rates (0.2 deg per min for 28). It was confirmed that Ti3Rhs and Hf3Rh5 have similar diffraction patterns, and that an alloy with the composition Zr3Rhs has a different pattern. Six Zr-Fh alloys with 59 to 69 at. pct Rh were therefore prepared and investigated in the as-cast state by X-ray diffraction and metallography. Alloys at 59 and 61 at. pct Rh were found to be a single phase, with the distorted B2-CsC1 type structure typical for the off-stoichio- metric region of the phase (Zr,-,Rh,)Rh. This phase forms a eutectic with ZrRhs at about 66 at. pct Rh: accordingly, alloys between 61 and 69 pct at. pct Rh consisted of two phases. There is no evidence for the existence of Zr3Rh5. Based on the results in Rafs. 1 and 5, on the present work on Zr-Rh, and on several additional alloys investigated, the portions between the AB and AB3 stoi-chiometry for Ti-Rh, Zr-Rh, and Hf-Rh are as follows: Further, several ternary alloys near Ti3Rhs and Hf,Rhs were prepared in which it was attempted to replace titanium and hafnium partly by zirconium, niobium, tantalum, and germanium. The results will be discussed in a later section. Structure Determination of Ti3Rh5. Since Ti3Rh5 and Hf3Rh5 are isostructural, the following discussion will largely deal with the former. Although the powder pattern of TisRhs is complex, as found previously,1 it could be indexed by comparison with other structures of A3Bs stoichiometry. Ti3Rh5 was found to be isostructural with Ge3Rh5, whose orthorhombic structure had been elucidated by Geller.9 As both the sizes and atomic numbers of germanium and titanium are comparable, the unit cell volume and the peak intensities could be expected to be similar; however, significant differences exist in the atomic positions, as will be shown. All lines in the powder patterns of Ti3Rh5 and Hf3Rhj could be indexed with primitive orthorhombic unit cells with the lattice constants: The fractional errors are 10 The low-angle portion of the indexed powder pattern of Ti3Rh with sin2 8 < 0.30 is listed in Table I. The extinction laws Okl only with k = 2n and hOl only with h - 2n are compatible with the space group Pbo2 and the more symmetrical space group Phnm of Ge3Rh5. Finally, the positional parameters of Ti3Rh5 and HfsRhs were refined under the assumption that titanium and hafnium occupy the germanium positions in Ge3Rh5. Integrated intensities were obtained from the diffraction patterns by planimetry. Intensities of overlapping reflections were separated by an iteration process incorporated into the least-squares positional refinement program according to a method described previously. The intensities of Ge3Rh5 were used in the first separation cycle, while the atomic parameters of Ge3Rh5 were used as starting values in the first refinement cycle. Absorption due to specimen

Jan 1, 1970

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.&apos; The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of &apos; However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-&apos; have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h&apos;) formed by the reaction where, accorhng to the notation of Kroger and Vink,6&apos;7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i&apos; and Fe3&apos; ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.&apos;-&apos; A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i&apos; and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By B. S. Hickman

Using primarily quantitative single crystal X-ray techniques studies have been made of the precipitation of the metastable w phase in alloys of titanium with Mo, Mn, Fe, Cr, and Nb. It is shown that, in agreement with earlier work on the Ti-V system, the composition of the w phase during aging approaches a constant; the value varies from one system to another in a systematic manner with the electron concentmtion. Results relevant to the mechanism of w precipitation during quenching and during aging are presented and discussed. Results are presented to confirm that the w phase is coherent and the nzorphology of the Necipitates is described and discussed. PRECIPITATION of the metastable w phase in alloys of titanium is of interest because of its severe embrittling effect and also because of the enhancement of the superconducting properties which accompanies precipitation.1 The general features of w phase precipitation have been discussed by cuillan and by Bagaratskii et d3 The work described in this paper forms part of a general study of w phase precipitation which was undertaken to elucidate various unknown or controversial features of the process, namely: i) What is the mechanism of formation of the phase ii) How does its composition, morphology, volume fraction, and particle size vary with the type and content of the alloying element and with the heat treatment conditions? iii) What is the relation between the w phase and the equilibrium a phase? In a previous paper4 the results of a detailed study of w phase in Ti-V alloys were presented. It was shown that: U During aging the composition of the w phase approached a saturation value of 13.5 to 14.0 at. pct V. ii) w precipitated as cube shaped particles and once precipitation was complete, particle coarsening did not occur. iii) a phase formed initially by direct conversion of w-phase precipitates. In this paper similar measurements are reported on Ti-Mo alloys and some more limited data given on the Ti-Cr, Ti-Fe, Ti-Mn, and Ti-Nb systems. The results i.1 the six systems are then compared. It has been shown previously by electron microscopy that the w precipitates as ellipsoids in both the Ti-Nb system,&apos; and in i-o.&apos; Blackburn and williamsz3 have reported the precipitates in Ti-Fe, Ti-Cr, and Ti-Mn are cubic, i.e., similar to the Ti-V system.476 EXPERIMENTAL METHODS 1) Specimen Preparation. Samples of the compositions shown in Table I were prepared by arc melting. High purity electron beam zone refined titanium (Materials Research Corporation Grade I—total impurity content =250 ppm) was used; the other source materials are given in the table. A commercial Ti-8 wt pct Mn alloy was used for studies of this system. After homogenization the materials were rolled or cut into strip approximately 1/4 in. by 2 in.; the strip was then heated at temperatures of 1200" to 1300°C for several hours by passage of a direct current through the strip in an ultra high vacuum system (<10-torr) and then quenched by admitting high purity helium and switching off the current. This treatment resulted in crystals up to 2 in. by 2 in. by A in., almost all of which had a [100] direction nearly perpendicular to the plane of the strip. The crystals were cut from the strip by spark machining and their composition checked by lattice parameter measurements supported by chemical analysis. 2) X-Ray Diffraction Methods. Lattice parameter measurements were made using a modification of the single crystal spectrometer described by ond. In this technique the crystal angles for reflection on either side of a highly collimated primary beam are measured. Generally the 400 CuK, or the 400 CuKp reflections of the bcc lattice were used. In the as-quenched crystals a precision of 1 in 105 was obtained, but due to line broadening the parameters in aged materials could only be measured to 1 in lo4. This accuracy was, however, quite adequate for the purposes of these experiments and enabled the composition of the p phase to be obtained to 10.1 pct in all systems except Ti-Nb where the lattice parameter change with composition is very small. The precipitation and growth of the w phase was examined using a single crystal goniometer attached to a Phillips diffractometer. The relative intensities and line shapes of b-phase and w-phase reflections

Jan 1, 1970

By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1&apos;&apos; and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5&apos;" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

Jan 1, 1970

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole&apos;&apos;) and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-&apos;) is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-&apos; using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- &apos; torr, Maiya and lakel measured y as 39 kcal mole-&apos; using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-&apos;: there is evidence also for a low temperature value of about 20 kcal mole-&apos;. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.&apos;-&apos;&apos; Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A&apos;, C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2&apos;3 M = mass of an evaporating molecule

Jan 1, 1970

By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.&apos; He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger&apos;s study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970

By A. R. Marder

Fe-C alloys have been investigated at temperatures below the eutectoid transformation to determine whether the superplasticity phenomenon exists for these materials. As a result of void formation at the carbide-ferrite interfaces that led to void coalescence and premature failure, the large elongations characteristic of superplustic matem&apos;als did not develop. It had generally been assumed that the conditions for obtaining superplasticity include: a) T/Tm =0.5, b) a strain rate sensitivity of the flow stress that results in m s 0.3, and c) fine-grain structure. Although superphsticity was not observed in the alloys studied, stress-strain rate measurements indicated that an additional condition for the existence of superplasticitv in Fe-C allovs is that the fine-wain structure be equiaxed in agveement with previous results on Zn-Al al1oys. MANY investigations have been made on the hot deformation of iron-base alloys in order to obtain an understanding of the variables that may affect high-temperature strength and ductility.&apos;-6 However, only a few papers have studied the effect of carbon content on the high-temperature properties of iron-base alloys. Peretayat&apos;ko and Zaikov and Wallquist and carlen4 studied the effect of carbon on strength in the y temperature range, and recently Robbins, Shepard, and sherby6 studied the influence of carbon on the torsional behavior of iron in the a and cu-plus-cemen-tite temperature ranges. In addition to studying hot deformation behavior, current investigations have also been concerned with the phenomenon of superplasticity in nonferrous materials, and, in particular, ferrous alloys. Superplasticity is identified by the increased resistance to necking that results from a high strain rate sensitivity of the flow tress. ackofenr proposed the strain rate hardening coefficient m = d log a/d log e as a measure of strain rate sensitivity and showed that m must be "-0.3 for superplasticity to exist. In addition, a fine-grained microstrcture,- a eutectic or eutectoid ornosition,- and a test temperature in the creep range (TITm > 0.5)" have also been advanced as necessary conditions for superplasticity. Although many workers""23 investigated superplasticity associated with the allotropic transformation in iron and the eutectoid transformation in steel, and recently chadler " and orrison have studied superplasticity in the a - y phase region, no one has measured the superplastic effect in the a + cementite temperature region. Therefore, the purpose of this investiga- tion was to determine the effect of carbon content, microstructure, and test temperature on the strain rate sensitivity of Fe-C alloys at temperatures below the eulectoid transformation. EXPERIMENTAL PROCEDURE Fe-C alloys with carbon contents of 0.2, 0.4, 0.6, 0.8, and 1.0 wt pct were prepared as 100 lb 54 in. ingots by vacuum-induction melting. The compositions are listed in Table I. All the ingots were soaked at 2100°F for 2 hr prior to rolling to 4 in. plate. The minimum finishing temperature for rolling was 1800°F. The plate was sheared in 10-in. lengths and tensile bars were rough-machined prior to heat treatment. The samples were heat-treated according to the schedule in Table I1 in order to obtain a fine-grained microstructure consisting of finely dispersed carbides in a matrix of small ferrite grains. All the tensile specimens were heat-treated prior to finish machining, and tensile testing was accomplished on an Instron machine in conjunction with a clamshell furnace. The buttonhead specimen configuration is shown in Fig. 1. An inert atmosphere, helium, was maintained during testing with a steel tube shroud in a bell jar arrangement. Predried helium was continually purged over the buttonhead specimens and exhausted through ceramic fiber at the bottom of the tube to keep oxidation at a minimum and to prevent

Jan 1, 1970

By P. S. Kotval, O. H. Nestor

Stacking fault energy measurements of nickel-base alloys have been mainly confined to binary and ternary systems. In this paper, the stacking fault energy has been measured by the rolling texture method in a series of ten alloys which comprise successive additions of Cr, Mo, Fe, and C to pure nickel, eventually resulting in an alloy of the composition of Hastelloy alloy X. The alloys studied here are single-phase, solid solutions with the exception of two alloys in which some undissolved particles of "primary" carbide have been retained. It is found that successive additions of chromium, molybdenum, and iron all lower the stacking fault energy, with iron having only a minor effect. The stacking fault energy is found to increase when carbon is added in solid solution. The results from the rolling texture measurements are correlated with thin foil observations of dislocation substructures in these alloys. In a recent paper&apos; it was pointed out that the dislocation substructure of various superalloy matrices could be classified into three broad categories based on &apos;high&apos;, &apos;medium&apos;, and &apos;low&apos; stacking fault energy. It has also been demonstrated2 that the dislocation substructure in each of these categories has a well defined role in the nucleation of strengthening precipitates which is different from the role played by the dislocation substructure in other categories. Thus, it becomes desirable to understand the influence of various solute elements on the stacking fault energy and hence on the dislocation substructure of the matrix, before any further development of superalloys by mi-crostructural predesign can be undertaken. Recently, Beeston and France have studied the influence of increasing solute additions on the stacking fault energy of a series of binary nickel-base alloys relevant to the Nimonic series using the rolling texture method, and have then estimated the effect of a given alloy addition in five commercial Nimonic alloys. However, comparison with stacking fault energy data from other investigations&apos;&apos;5 suggests that the influence of a given solute element in a nickel-base binary system is not necessarily the same in a ternary or more complex superalloy system. Accordingly, the present work was undertaken to study the effect of successive addition of solute elements to pure nickel, the final composition being the nominal composition of Hastelloy X. The rolling texture method of stacking fault energy measurement was used since it can be used for the whole range of stacking fault energy values and does not have the disadvantage of, say, the Node method which is only applicable to low values of stacking fault energy. In addition, the rolling texture method provides a means of determining the stacking fault energy which is statistically more significant than that provided by other methods. EXPERIMENTAL TECHNIQUES Button heats of alloys of the compositions shown in Table I were prepared. Each button was remelted not less than four times. After a slight deformation (approximately 5 pct) all alloys were homogenized at 2200°F except alloys, H . I, and J. Alloys H and I were solution heat treated at 2150°F and alloy J at 2282OF. The buttons were cold worked by rolling, using "end-to-end" passes and intermediate anneals at the homogenization temperatures mentioned above. After each annealing treatment the samples were rapidly water quenched to avoid any precipitation. In alloys F and I, however, a few particles of "primary" carbides were retained even after the homogenization treatments at the temperatures mentioned above. Part of the solution heat treated material was cold worked to 0.04-in.-thick sheet and the penultimate reduction was -50 pct of deformation as recommended by Dillamore et al. All annealing was carried out in vacuo within sealed quartz capsules. Some of the material from each alloy was rolled down further to 0.004 in. strip for thin foil transmission electron microscopy specimens. Specimens of this strip were annealed at the homogenization temperature for 1 hr and then strained 7 pct by rolling at room temperature. Thin foils were prepared from the strip specimens by the &apos;window" technique using an Ethanol-Perchloric acid electrolyte at 32°F and a voltage of 22 v. Stainless steel cathodes were employed. All transmission electron microscopy was performed in a JEM-7 electron microscope using an accelerating voltage of 100 kv. Specimens from the 0.04 in. sheet which had been rolled -60 pct in the final pass were electropolished to remove the surface layers to a depth of approximately 0.002 in. Rolling texture pole figures for all the alloys were determined using a Schulz ring and nickel filtered CuKa radiation at 50 kv and 20 ma. The texture parameter Io/(lo + I,,) (where Io is the

Jan 1, 1970

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400&apos;F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y&apos; precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y&apos; precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10&apos; to 10&apos; cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975&apos;F for 4 hr.

Jan 1, 1970

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970