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By R. H. Frazier, C. H. Lorig, F. W. Boulger

THERE are both advantages and disadvantages in using semikilled steels in place of killed steels. One advantage of semikilled steels is they provide a higher ingot-to-product yield. This is especially important to shipbuilders in the time of national emergency. By using semikilled steel for hull plates, a greater number of ships can be built from the same ingot tonnage. Consequently, if semikilled steel plates are adequate for the service, the advantage of the higher product yield is of considerable importance. The performance of hull plates is closely associated with the ductile-to-brittle transition temperature, and this, in turn, is strongly dependent on the composition of the steel. A low transition temperature is desirable because it indicates that the steel is less likely to fail at low ambient temperatures. Killed steels are known to have lower transition temperatures than semikilled steels. It is believed that the better qualities of killed steels in this respect are due mainly to the low oxygen contents of the steel. The principal deoxidizers, aluminum, silicon, and manganese, lower the oxygen content. Fundamental studies1-0 have shown that the oxygen content remaining after the addition of one of these three elements is influenced by the residual amounts of the other two present. In the current study, therefore, various amounts of silicon and aluminum were added to steels containing different manganese contents for the purpose of studying the influence of silicon and aluminum on the notched-bar properties of hot-rolled steels. Eleven types of steels were studied. The temperature at which the plates were finish-rolled was care- fully controlled at 1850°F. All plates were rolled to ¾-in. thickness, and tested in the as-rolled condition. The total number of steels prepared in the laboratory for this study was 95. The charge consisting of ingot iron and ferrosilicon equivalent to 0.10 pct Si was melted in a 200-lb induction furnace under an atmosphere of argon to insure low, uniform nitrogen contents. After the charge was melted and the desired temperature was obtained, the melt was partly deoxidized with either silicomanganese or aluminum. Aluminum was used for this purpose in only those steels with very low silicon contents, where the finished steel was to contain some aluminum. This initial deoxidizing addition was made to obtain consistent recoveries of subsequent additions of ferro-manganese, ferrosilicon, and aluminum. Carbon, in the form of graphite, was added, either just prior to tap or to the final aluminum addition. The entire heat of 200 lb was poured directly into a 6x6-in. big-end-up mold. The ingots of semikilled steel were capped with a steel plate. The killed steels, on the other hand, were poured with a hot-top containing 14 pct of the total volume of the ingot. The ingots were processed by heating to 2250°F, followed by forging to slabs 1¾ in. thick and 6 in. wide. After reheating to 2250°F, the slabs were rolled to 0.9-in. gage, using reductions of approximately 1/6 in. per pass. The 0.9-in. thick plates were immediately recharged in a furnace held at 1850°F. After 30 min in the furnace at 1850°F, the plates were rolled to ¾ in. in one pass. Following the final pass, the plates were stacked on edge on a brick floor, with a brick separating one from another, where they were allowed to cool in air. Drillings for chemical analysis were taken from the plates at locations corresponding to the top and bottom of each ingot. Carbon, manganese, silicon, phosphorus, sulfur, and nitrogen contents of each sample were determined. The analysis of each steel was carefully controlled so that the contents of

Jan 1, 1957

By Craig R. Barrett, Oleg D. Sherby

The creep characteristics of four pure metals with widely Varying stacking-fault energies (silver, copper, nickel, and aluminum) were evaluated above 0.5Tm. Creep tests were performed under conditions of constant atomic diffusivity and constant stress over the elaslic modulus. The sleady-state creep rate, Es, was found to he a funclion of the THE most common empirical representation of the steady-state creep rate, Es, at high temperatures and intermediate stresses is of the form where a is the applied stress, E is an elastic constant, A and n are constants (n is typically stacking-fault energ, y, such that Es is proportional to y3,5. In addition, it was uncovered that the primary creep strain and the strain to fracture increased with increasing y, and that the ratio of initial to steady-state creep rate decreased with increasing y. about 5), Q is the activation energy for creep (usually equal to that for self-diffusion), and kT has its usual meaning. sherbyl and McLean and ale' have used this expression to correlate creep data for a number of pure metals. An interesting aspect of Eq. [I] is the absence of any dependence on the stacking-fault energy. While most creep data seem to obey the stress and temperature dependence predicted by Eq. [I], when data for several metals are put on a master plot they do not fall on a common line but form a band. The width of this band corresponds to a variation in Es of 102 to l03. sherbyl attempted to explain this band by assuming that a grain-size effect was present which led to the observed variation. On the other hand, Felt-

Jan 1, 1965

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The effect of machine stiffness on discontinuous flow and fracture of the 2024 aluminum alloy was studied in tension at 4.2OK. An increase of machine stiffness was found to decrease the amount of elongation and drop in load during discontinuous flow, thereby postponing fracture to larger strains and higher stresses. The possibility of utilizing stiffened tools in deformation processing to suppress shear fracture originating from unstable flow was indicated. The problem of nucleating discontinuous flow and the role of the effective mass of the system in discontinuous flow were also considered. AT low temperatures the plastic flow of metals is often discontinuous, with sudden load drops and elongations.1,3 Basinski1,4 has presented strong evidence that discontinuous flow, at least in aluminum alloys, occurs under nearly adiabatic conditions. During testing the load may drop suddenly and flow become localized when the thermal softening, due to heat generated in plastic straining, is greater than the strain and strain-rate hardening. This instability criterion is more easily satisfied at low temperatures because 1) the volume specific heat is reduced so that relatively large temperature increases are possible in straining, and 2) the flow stress is relatively temperature-dependent. The important role of adiabatic shear in ductile fracture processes has been emphasized,5-1 and consideration has already been given to the influences of thermal and mechanical properties on the tendency of a material to undergo adiabatic shear.17677 By focusing attention on how the mechanical loading system influences low-temperature discontinuous flow, additional insight into adiabatic shear and its effect on fracture may be gained. EXPERIMENTAL PROCEDURE Because of its low thermal conductivity, the 2024 aluminum alloy exhibits a highly consistent discon- tinuous-flow behavior at 4.2°K and was therefore chosen as the material for study. Machined specimens of 0.113 in. diam and 1.125 in. gage length were solution heat-treated at 490°C for 3 hr, quenched into cold water, and immediately immersed in liquid nitrogen until just before testing. Testing was done at 4.2°K by immersion in liquid helium at a crosshead drive rate of 0.03 in. per min. As normally used (hard-machine basis), the spring constant of the testing machine was k = 25,000 lb per in. By inserting beam springs in series with the specimen, this value could be lowered by a factor of about 100. Details can be found elsewhere.? As a result of variable machine stiffness, the actual strain rate ranged from about 3 x 10 5 to 3 x 10-4 per sec from one test to another, as well as within any one test. However, preliminary tests had established that the tensile curves were not altered significantly by this strain-rate variation. Fig. 1 shows a typical load vs plastic-elongation curve for a solution heat-treated 2024 aluminum alloy specimen pulled in the standard hard machine (k = 25,000 lb per in.) at 4.2"K. The elastic extension has been subtracted. Plastic flow proceeded smoothly from yielding at approximately 22,000 psi (load = 220 lb) to a strain of about 4 pct at which point the flow became discontinuous. The magnitude of the load drops as well as the plastic elongation per drop increased with increasing strain until the specimen finally broke abruptly. The load-elongation behavior of a sample tested with a relatively soft machine under otherwise identical conditions is given in Fig. 2. In general, there

Jan 1, 1964

By H. Yoshida, B. G. Liebmann, R. E. Green

In recent years considerable work has been undertaken in order to gain an understanding of the mechanisms responsible for the generation of recrystal- lization textures in face-centered-cubic metals. Two theories have been proposed, that of oriented growth1 and that of oriented nucleation,' and several attempts have been made to check these theories directly by recrystallizing deformed single crystals.3-5 Two groups, Graham-Cahn and Liebmann-Liicke-Masing, studied the orientation of recrystallized grains and their rate of growth, both using strained aluminum single crystals of commercial purity (Graham et al., 99.6 pct, Liebmann et al., 99.8 pct). Surprisingly, the results obtained by the two groups were completely

Jan 1, 1960

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"' or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

By P. J. Soltis

Direct as well as indirect evidence of a-phase ordering was found in a "near-a" type titanium alloy, Ti-8Al-1Mo-1V. The annealed alloy showed an anomalous decrease in second-stage creep rate at 950°F (510°C) and 47,500 psi. Anomalous increases were noted in initial yield stress after 500 hr creep exposure and in tensile strength after 1100 hr creep exposure. Debye-Scherrer X-ray diffraction patterns obtained on fine-grained polycrystalline speci-ment showed much line broadening and development of superlattice lines after 500 hr at 510° C. Examination with the light and electron microscopes failed to reveal phase changes in thermally exposed material, but detailed metallography is presented illustrating the plastic and fracture characteristics of the alloy. Electron-metallographic evidence is presented, however, which shows the nature of the nucleation and growth of ordered regions from the disordered a in annealed material. In the original phase diagram of the binary Ti-Al system constructed by Ogden et al.1 aluminum was shown to be soluble in a titanium over a wide temperature range at concentrations up to about 30 pct. Subsequently, a number of papers2-7 have appeared which indicate the existence of either intermetallic compounds and/or ordered phases in the a field up to 25 pct Al. In the most recent of these, Goldak and Gordon paw7 have determined unequivocally the ordered hexagonal D019 structure for Ti3Al in a 25 pct Al alloy. No superlattice lines were observed above 1112°F (600°C). Previously, the embrittle-ment encountered by Crossley and Carew4 in low- temperature heat treatments of binary Ti-Al alloys low in aluminum had been attributed to the appearance of a new phase in light micrographs. In the present work, direct as well as indirect evidence is presented showing the existence of a-phase ordering in what is essentially the binary Ti-8A1 alloy containing small percentages of the ß stabilizers molybdenum and vanadium, i.e., the "near-a" Ti-8Al-1Mo-1V alloy. Although Bohanek and Kessler8 have shown that this alloy has good stability at temperatures up to 1100°F (593°C), the present work shows instability at 950°F (510°C) where long exposure times were used. Light and electron microscopy proved very useful in revealing the mechanical behavior of ordered a and led to the conviction that ordered "near-a" alloys may have remarkably good properties and useful engineering applications.

Jan 1, 1965

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By P. G. Shewmon

If interfacial equilibrium is maintained at the interface between a growing precipitate and the supersaturated matrix, so that solute diffusion alone determines the growth rate, the precipitate shape should evolve toward that characteristic of the dendrites found in solidification. However, this shape is rarely observed in precipitation reactions proceeding at high temperatures where interfacial equilibrium is usually felt to prevail. Thus some other stabilizing factor must enter, to keep the interface smooth. It is shown that a slow interfacial reaction (low interfacial mobility) will stabilize the interface, while transformation stresses have a IN studying the kinetics of phase transformations such as solidification or proeutectoid precipitation at high temperatures, it is customary to assume that equilibrium exists across the interface and that the rate of the reaction is determined by the rate at which heat and solute diffuse to and from the interface. In the case of precipitation, such an assumption predicts an almost infinite rate of initial growth. It is generally stated that the rate cannot be infinite and that during some initial period the rate must be determined not by solute diffusion but by an interfacial reaction, i.e., transferring atoms across the interface. The duration of this much weaker stabilizing eFfect and impurities tend to enhance instability. It is also concluded that a sets an upper limit on the wavelength of the perturbation that can give instability. Thus initially all flat or smoothly curved particle interfaces will be stable even if their growth is diffusion-controlled. Proeutectoid precipitation in the Fe-C system is considered in some detail and it is shown that the experimental results can only be rationalized if the growth rate of ferrite in steel transformations is determined by a slow interfacial reaction for all hut a few orientations between the two phases. initial period has never been clearly established, but it is generally assumed to be too short to affect any measurable results.' Several authors have pointed out that in the case of interfacial equilibrium any bump in the surface will grow out ahead of the planar interface due to the higher gradient in front of it.2j3 Thus the interface will be unstable with respect to an irregular interface with points (plates) propagating rapidly out ahead of the interface into the supersaturated phase. Recently, Mullins and Sekerka have given equations for the stabilizing effect of surface tenion.~ They found that for particles with a radius of curvature of 1 p or greater the stabilizing effect of surface tension will be completely overcome by a supercooling, or supersaturation, of as little as

Jan 1, 1965

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By A. N. Holden, W. E. Seymour

DURING the last several years, the U-Zr system has been studied at many laboratories as one of the research programs sponsored by the Atomic Energy Commission. The equilibria in part of this system have been difficult to determine, although the phase diagram from 0 to 60 atomic pct Zr has been established with reasonable certainty. Existing diagrams of the system vary appreciably beyond 60 atomic pct Zr, particularly with regard to the existence of an intermediate phase. Most existing diagrams show a transformation or reaction horizontal near 600°C. In 1955, a collection of uranium phase diagrams' was prepared at the Battelle Memorial Institute and the U-Zr diagram in that collection contained a questionable region in the vicinity of 60 to 80 atomic pct Zr. Summer-Smith" has published a phase diagram of the system that shows no intermediate phase. Summer-Smith did his work with powders and found only the uranium and zirconium eutectoid mixture from X-ray patterns of material annealed below 600°C. Mueller3 at Argonne National Laboratory did similar work with filings, and he found that initially there was a pattern of an intermediate phase, but on long-time annealing

Jan 1, 1957

By A. T. Aldred

HIS note reports the existence of several new scandium intermetallic compounds of the A2B and AB stoichiometries where the A element is scandium and the B element is from group VIII or IB of the periodic table. Alloys were arc melted from high-purity materials using 2-g charges. Typical lot analyses for the materials used are given in Table I. Chemical analyses were not made on the alloys as there was little or no weight loss on melting. After annealing the specimens for 14 days at 600°C and water quenching, metallographic and X-ray techniques were used to determine the occurrence of the various phases. Table II lists the relevant data for the A2B phases. The Ti2Ni structure,2 has ninety-six atoms in a face-centered cubic cell, whilst the Al2Cu structure is body-centered tetragonal.3 The occurrence and stability of the various A2B type phases in transition metal alloy systems has recently been considered by Nevitt.4 The Ti2 Ni-type phases occur over a relatively narrow range of radius ratios from 1.14-1.26 with A partners mainly from the titanium group and B partners predominantly from the cobalt group. This suggests that both a favorable relative size of the atoms and a favorable electron concentration are necessary conditions for the existence of this structure type. A12Cu-type phases involving Ti group elements as A partners are formed with B partners from the cobalt and nickel groups, predominantly the latter, and have a higher radius ratio (1.27-1.29) than the Ti2Ni-type phases. The occurrence of both Sc2Pd and Sc2Co can be rationalized in terms of these considerations but SczNi is anomalous because of its high radius ratio. The radius ratios are calculated from the Goldschmidt CN12 radii and it might be postulated that the scandium atom is reduced in size in the compound. Unfortunately the apparent atomic size of scandium in the compound cannot be calculated from a knowledge of the structure and lattice dimensions. The crystal structure of the Sc2Au compound could not be identified from the powder diffraction pattern, but it is interesting to note that it is isostructural with a series of A2Au phases where A is a rare earth element.5 Pertinent information concerning the AB phases found in this investigation is given in Table 111. All the phases have the ordered bcc CsCl structure. The occurrence and stability of CsC1-type phases have recently been discussed by Dwight,7 who concludes that the relative sizes of the atoms do not appear to be a controlling factor (the radius ratios of all the known phases vary between 0.985 and 1.439) but that the occurrence of the phase is predominantly dependent on the relative positions of the A and B partners in the periodic table. As a measure of the stability of a given CsCl phase it has been customary to define a lattice contraction on alloying, DAB — dAB, where DAB is the AB interatomic spacing as calculated from the Goldschmidt CN8 radii and dAB is the AB interatomic distance in the compound (= v3/2 ao). Values of the parameter DscB -dScB for the compounds found in this investigation are given in column 5 of Table III and are plotted in Fig. 1. If the lattice contraction does in fact reflect the stability of a phase then Fig. 1 shows two very interesting trends when the position of the B partner in the periodic table is considered. Firstly, within any given group the stability increases in order on going from the first to third long period. Secondly, within any given period the stability increases in order as the B partner is taken from the copper, nickel, and cobalt groups. In the case of the second long period, the lattice contraction reaches a maximum at ScRh and then decreases to ScRu. The same trend could

Jan 1, 1962

By Eric Kula, Åke Josefsson

L. J. Dijkstra and R. Sladek, (Ontario Research Foundation, Toronto, and Institute for the Study of Metals, Chicago, respectively)—This interesting paper confirms some results obtained some years ago in collaboration with Fast: namely the broadening of the nitrogen peak by the presence of small amounts of manganese. Later on a more extensive study of this effect was made at the Institute for the Study of Metals at Chicago. As the work has not yet been submitted for publication we wish to mention here briefly some of the results. The effect of about 0.5 atomic pct manganese, chromium, molybdenum, or vanadium on the nitrogen-peak in iron was examined. The broadening found previously in the case of manganese was even found to be more pronounced for chromium. In the case of molybdenum and vanadium a double peak was observed which seemed to justify the idea that in all cases mainly two relaxation times were involved: namely, the normal relaxation time as found in pure iron and a second relaxation time related to the existence of abnormal interstitial lattice sites introduced by the foreign metallic element. The analysis showed that for the normal nitrogen-peak as a reference at 22°C the abnormal peak was found at about 32°, 47°, 75°, and 87°C in the case of manganese, chromium, molybdenum, and vanadium, respestively. In the manganese alloy the free energy difference for a nitrogen-atom at an abnormal and a normal lattice site was estimated at 2800 cal per mol. This means that for temperatures above 100°C the solid solubility and overall diffusion rate of nitrogen is not much affected by additions of 0.5 pct Mn. We believe that the difference in rate of precipitation of nitrogen in pure iron and the manganese alloy is mainly a question of the number of potential nuclei available in the different steels. In studying the effect of these alloying elements on precipitation of nitrogen, a distinction must be made between the para reaction and ortho reaction, using terminology introduced by Hultgren.7 The ortho reaction in which the alloying metallic element participates in the diffusion under formation of nitrides occurs at high temperatures such as 600°C. The para reaction in which the alloying metallic element does not diffuse and in which the nitride inherits its alloy content from the matrix occurs at lower temperatures. To prevent the ortho reaction the alloys have to be quenched rapidly from the phase. It is not surprising that the authors find that the height of the peak indicates a lower nitrogen content than chemical analysis. In the first place the peak is not a single relaxation peak and secondly, the steels were not quenched from the phase after the nitrogen was introduced at 580 °C.

Jan 1, 1953

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger's grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger' s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By Edward J. Felten

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.' In an earlier report,' the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high

Jan 1, 1962

By Paul A. Beck, M. N. Parthasarathi

By determining the (220) pole figure for OFHC copper rolled to 96 pct R. .A., the occurrence of four texture components of the type (135) [211] was confirmed. It was found that the total volume fraction of material close to the four symmetrical orientations of this type is larger than the volume fraction of the other components put together. THE rolling texture of copper was described by early investigators1'" as a mixture of components of the (110)[l12] and (112) [11l] types. Other studies, still using the qualitative photographic method of texture determination arrived, instead, at orientations of the type (135) [533] or (135) [211] for copper3'4 and at the closely related "Z-texture" for a fee nickel-iron alloy.5 The prevalence of this type of orientation, near (123) [412], in the rolling texture of aluminum and of copper was later confirmed by means of quantitative diffractometer methods.' However, in a recent paper7 Jones and Fell stated that the (110) [112] and (112) [111] double texture was in better agreement with the measurements of Young's modulus for cold-rolled copper.' These authors also expressed their belief that the "roll texture" can be determined by means of two photographic quasi-fiber texture patterns taken with sheet specimens rotated around the rolling direction and the transverse direction, respectively. Jones and Fell found7 that the results obtained from such patterns for cold-rolled nickel did not agree with any of the orientations mentioned above, but they suggested that the observed diffraction spots may have been brought about by the overlapping of reflections due to the (110) [112] and (112) [11l] double texture components. Jones and Fell concluded that the (123) 14121 type orientation is inconsistent with their patterns. They also stated, without offering any supporting evidence, that this orientation is inconsistent with the (220) pole figure. "Ideal orientations" are often used for a very rough description of the principal orientations encountered in a texture, It is, however, well to remember the fact that, no matter how "accurate", these ideal orientations are only schematic representatives of a continuous distribution9, which often (as in the case of rolled copper) includes extensive orientation spreads. The attempt by Jones and Fell7 to use elastic modulus data in deciding between various ideal orientations in the rolling texture of copper neglects this fact. The inadequacy of two-dimensional "axis density figures" in describing orientation distributions in sheet textures was previously discussed.9 It was also pointed out9 that there is no reliable evidence to prove that orientation distributions derived by the "quasi-fiber method" from rotated sheet specimens are fully equivalent to the corresponding information obtainable from quantitative pole figures. The view that a sheet texture could be adequately determined by means of two photographic quasi-fiber texture patterns is obviously erroneous9. The question as to the consistency with the (220) pole figure of ideal orientations derived from the (111) and (200) pole figures is, on the other hand, certainly very relevant. Since no quantitative (220) pole figure for cold-rolled copper appears to be available in the literature, the following work was undertaken. EXPERIMENTAL METHOD An extruded rod of OFHC copper, 1 in. in diam, was given alternate rolling (30 to 35 pct R.A.) and

Jan 1, 1962

By W. C. Hagel, H. J. Beattie

Seven austenitic alloys of varions base compositions and minor-alloy additions were solution-treated, aged systematically between 1200oand 1800oF, and examined by X-ray and electron metallography. Intragranular preczpitations of µ, Laves, s, ?', Ni3Ti, and x phases were observed as a function of composition and aging time and temperatwre. Phase solubility limits were detevtnitzed within 100Fo intervals. These inter metallic compounds fall into two distinct general classes, and whichever class predomznates depends on base composition. It has become increasingly evident that multicom-ponent austenitic alloys are well characterized by their precipitation processes. Since certain groups of elements act as one, the relationships among these processes are reasonably simple; complete identification of such processes is usually attainable by a systematic aging study with a combination of techniques centered on microscopy and diffraction. Several nickel- and cobalt-base alloys illustrating cellular precipitation and its interaction with general precipitation were reported previously.1 The group of alloys covered in the present paper demonstrates precipitation-hardening reactions involving two distinct classes of intermetallic compounds where the predominating class appears to depend on base composition. This dependency ties in with a crystal-chemistry regularity first observed some twenty years ago by Laves and Wallbaum but never amplified to our knowledge. Results of electron-microscope and X-ray diffraction studies on systematically aged hot-rolled alloys known commercially as S-816, S-590, Rene-41, Incoloy-901, M-308, and M-647 are reported here. Some of these alloys have previously undergone minor-phase analyses by other investiators. Alloy S-816 was investigated by Rosenbaum, Lane and Grant,3 and Weeton and Signorelli.4 Rosenbaum found only CbC in hot-rolled bars. Lane and Grant found CbC and a small amount of M6C in the cast structure and stated that both carbides form during aging, most of the precipitation being CbC. Weeton and Signorelli found CbC, M23C6 and a weak indication of a phase after a slow step-down cooling cycle from 2250°F. Rosenbaum also investigated hot-rolled samples of S-590 and identified CbC and M6C. Preliminary information on Rene-41, gained partly from the present work, was reported by Morris.5 Long-time precipitation phenomena in Incoloy-901 at 1350°Fwere investigated by Clark and Iwanski.B heir raw data re- semble those of our present heat with 0.1 pct B, while their interpretation of these data resembles our interpretation of data from another heat with only 0.001 pct B; they made no statement as to boron content. No previous minor-phase studies of alloys M-308 or M-647 have been reported. EXPERIMENTAL METHODS Table I gives alloy compositions in both weight and atomic percent. Specimens were solution-treated from 1700º to 2200ºF, aged at logarithmic-time intervals up to 1000 hours between 1200 and 1800 F, and examined in accordance with procedures previously described in detail. ' ' Phase extractions were carried out in electrolytic cells containing 800 ml of either 7 pct HC1 in denatured ethanol or 20 pct H3PO4 in water. After electrolysis for 48 hr at 0.1 to 0.2 amp per sq inch, residues were separated by filtration or centrifuging. X-ray powder patterns of residues were recorded on a diffractometer for accuracy and on film for sensitivity. Lattice parameters were calculated by least-squares analyses of indexed sin 8 values, and relative abundances were estimated from intensities of strongest lines of each phase. These phase abundances denote relative amounts with respect to each other rather than to the alloy. Mechanically polished specimens were etched in a freshly mixed solution of 92 pct HC1, 5 pct H2SO4, and 3 pct HNO3. Parlodion replicas for the electron microscope were chromium-shadowed in high vacuum at a glancing angle of 20deg. All electron micrographs are reproduced here with the shadowing source above. The correspondence betweenelectronmicrostructures and phases identified by X-rays was established by a high redundancy of correlation between relative amounts at different stages of aging and examination above and below critical transformation or solubility temperatures. EXPERIMENTAL RESULTS S-816 and S-590—The phases found in S-816 and S-590 after various aging and solutioning treatments are listed in Table 11. These data and the observed

Jan 1, 1962

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.' Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,' were added to the A1-Cu alloy. Test speci-

Jan 1, 1955