Search Documents

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By A. G. Guy, T. B. Lindemer

A second intepation of the Fick law has been developed and applied to three-place data generated from the Gosting and Fujita solution of the diffusion equation. This integration provides new mathematical techniques for the analysis of experimental data. Through use of the synthetic data it is shown that for concentration-independent interdifiusion coefficients these techniques permit a more accurate determination of the coefficients than does the usual Boltzmann-Alatano analysis. Another technique, applicable to the most general concentration-dependent diffusion coefficients , can be used to determine whether given sets of coefficients are consistent with the experimental ternary concentration-distance curves. DURING the past 10 years the subject of three-component diffusion has advanced from the stage of a laboratory curiosity to the status of an accepted portion of physical metallurgy.1 In the course of this development the underlying treatment for two-component sys- tems was extended and generalized to accommodate the added component, but fundamentally the analyses currently employed for ternary systems are analogous to those previously developed for binary systems. There are several indications that an improved analysis is needed for the ternary case. First, the two cross coefficients, D312 and D321 are typically an order of magnitude smaller than the direct coefficients and consequently are difficult to determine with adequate precision. Second, instead of a single concentration-penetration curve (as in binary diffusion), there are four such curves in the usual determination of ternary diffusion coefficients. These curves have definite theoretical interrelationships, but actual experimental curves exhibit significant departures from these relationships. Finally, the amount of data needed to adequately describe the diffusion behavior of a ternary system is so large that radically new methods are needed to facilitate the gathering of these data. ICirkaldy2j4 has proposed several possible analyses of ternary diffusion data, including some of the methods in current use. A "second-integration" procedure proposed by him4 differed in important respects from that presented here and was not carried to the point of application. Two other methods have been explored by the authors and will be published separately; these are a numerical analysis technique and a method for the analysis of a single ternary diffusion couple. Still other analyses are being explored by various investigators. At present it seems likely that the final analysis of ternary diffusion that evolves will be a composite

Jan 1, 1968

By William H. Hallahan

The Friedensville zinc mine of The New Jersey Zinc Company is located about four miles south of Bethlehem, Pennsylvania in the Saucon Valley, an infolded and down faulted block of Cambro-Ordovician carbonate sediments surrounded by hills of pre-Cambrian gneiss and Cambrian quartzite except where breached by Saucon Creek at its entrance into the Lehigh River. The Beekmantown formation of lower Ordovician age is the host for zinc and limonite ores, the former occurring in the lower dolomitic portion thereof and the latter in the upper interbedded dolomite and limestone portion of the section. The Beekmantown is overlain unconformably by the Jacksonburg of middle Ordovician age and according to Miller (2) underlain conformably by about 2500 feet of Cambrian dolomites and 200 feet of the basal Cambrian Hardyston quartzite. Igneous rocks, younger than the Cambro-Ordovician carbonate rocks, are absent in the vicinity of the ore deposits. The major structure is a N60°E-trending saddle-shaped doubly plunging anticline overturned to the north. A syncline lies to the north of the anticline. A thrust fault of substantial displacement repeats the south limb of the anticline. The ore consists of sphalerite and pyrite, along with gangue dolomite and quartz, filling and replacing the sedimentary type matrix of a strata-bound solution collapse breccia in the dolomitic portion of the lower Beekmantown. This breccia was produced in pre-Jacksonburg time as a consequence of uplift, erosion, and development of a karst topography and subsurface drainage system in the Beekmantown. Deposits of both zinc and limonite are present on the vertical north limb, on the crest and on the gently dipping (25°) south limb of the Friedensville anticline; consequently, there is no preferred structural setting for mineralization. Rather this distribution supports the view that the folding is post-ore. Features confirming this view are the development of flow cleavage in the breccia matrix, the deformation of some of the sphalerite, and the fracturing of the pyrite mineralization therein. There is nothing to indicate that the age of mineralization is other than Ordovician and older than Taconic deformation. In the absence of intrusive igneous activity younger than the ore host, the writer suggests that submarine volcanic exhalations associated with the volcanic activity recorded in the eastern eugeosynclinal facies of the Ordovician may be the source of the metal ions.

Jan 1, 1968

By R. L. Stone

None of the currently used methods of testing bentonites as binders for strengthening iron ore pellets is entirely adequate by itself. Since more knowledge was needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced, attention was paid to possible new techniques for rating bentonites. With the structural nature of bentonites — in particular, the montmorillonite component — the possibility of rating bentonites on the basis of zeta potential was investigated. These bentonites were also rated by conventional tests and measurements, including colloid content, barrel yield, pH, chemical analysis and physical tests on green and dry pellets. A mechanism for pellet bonding based on electro-kinetic forces between the bentonite and the iron ore concentrate appears to be feasible. In pelletizing, from 6 to 18 lbs of bentonite is added per ton of concentrate to give strength to the green and dry pellets. In some operations even more bentonite than is required for strengthening purposes must be added for moisture adsorption to pennit balling of the concentrate. Since bentonite is thus a major item in pelletizing, more knowledge about the way in which bentonites act as binders and better ways of rating this ability would help in the difficult job of selecting the right bentonite for a given concentrate. The fact of the matter is that although several methods are in current use for testing bentonites, none of these methods are consistently foolproof. For example, a given bentonite may rate high by several standard tests yet turn out to be a poor binder, and of course the reverse also occurs. Actually, more knowledge is needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced. In this study attention is therefore paid to possible new techniques for rating bentonites. With the structural nature of bentonites as a starting point, we investigated the possibility of rating bentonites on the basis of the zeta potential, i.e., the electrokinetic ootential on the montmorillonite colloids — the main component of bentonite binders. The zeta potential technique was applied to a range of commercial bentonites from several areas in the U.S. and abroad. These bentonites were also rated by conventional tests and measurements, including:

Jan 1, 1968

By Ramkrishna Agarwal

The problem of the measurement of in situ stresses in rock masses has, in recent years, become one of the prime concerns of investigators and researchers in the field of rock mechanics. Numerous instruments have been developed for that purpose and various techniques have been used to determine the absolute values of these stresses at a point.l The "stress-relief" technique has gained the widest acceptance. In its usual application it relies on one of the two following principles: (1) Measurements of the changes in a "solid inclusion" in a borehole,2 or (2) Measurements of the diametral deformation of a borehole with a free boundary." The theoretical development, in the case of the latter, is based upon an evaluation of the deformation of a circular hole in an infinite plate under the action of a uniaxial stress field. Expressions for the deformations may be obtained by using either the plain strain or the generalized plane stress theoretical approach of the classical theory of Elasticity, which assumes that the material is linearly elastic, homogeneous and isotropic. The solution for the case of a biaxial stress field is obtained by the Principal of Superposition. The circular hole becomes elliptical after deformation takes place under the action of a uniaxial or biaxial stress field applied to the plate. In the practical application of the technique, the reverse procedure is applied. A borehole is drilled in the rock and a deformation-measuring

Jan 1, 1968

Conventional hand drawn isopach maps of the cover of the Bulli Seam are too eomplex for use in the delineation of large domains of similar cover. Isopach maps prepared from trend surfaces fitted to the cover data are much simpler in form and so provide a convenient method of delineating broad domains of similar cover.

Jan 1, 1968

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

ABSTRACTRock stresses can be modified by physicochemical processes.If rock pores allow the ingress of water and oxygen, but are not large enough to permit the exit of larger molecules of weathering products, anomalous rock pressures develop. Rock masses may also be subjected to osmotic pressures developed as water diffuses into pores and joints filled with saline water. Anomalous rock pressures may also develop as gels filling pores undergo syneresis and as salts crystallize from pore solutions.

Jan 1, 1968

By S. C. Sun, T. Chao

The reaction of gaseous sulfur trioxide with different aluminum-bearing minerals for the conversion of their alumina content into water soluble sulfates has been investigated. Theoretical considerations indicate that this reaction is thermodynamically feasible and that preferential sulfatization can be accomplished. The five minerals tested were gibbsite, boehmite, diaspore, kaolinite, and halloysite. In general, over 90% sulfatization could be achieved in 1 hr when using sodium sulfate as an additive at a temperature between 500° and 600°C. It was found that sulfates of the light alkali and alkaline earth metals exhibited some effectiveness in promoting the sulfa-tizing reaction. Selective sulfatization of alumina in a mixture of calcined halloysite and ferric oxide was accomplished. The gas-solid type of sulfatizing reactions have become increasingly important in recent years for the treatment of the oxides of such nonferrous metals as cobalt,' nickel,' manganese,3 zinc, and copper.4-6 Similar reactions were attempted in the present investigation for the recovery of aluminum from the low grade aluminous ores. Unlike the Bayer process in which silica is a serious contaminant, or the acid processes whereby iron usually causes difficulties, the reactions between gaseous sulfur trioxide and various aluminous minerals could hopefully be selective for aluminum. THEORETICAL CONSIDERATIONS Reactions between aluminum-bearing minerals and gaseous sulfur trioxide have been shown respectively in Table I and Fig. 1 to be thermodynamically favorable for temperatures below 1000°K approximately. Calculations of the thermodynamic functions were where ?G, ?H, ?Cp and ?S are changes in free energy, enthalpy, constant-pressure specific heat, and entropy of the system under consideration, respectively; T is the absolute temperature, R the universal gas constant, and K the equilibrium constant. Thermochemical data so far available for these calculations were based on sources given by T. Chao.7 In Table I, the free energy values indicate that reactions between the gaseous sulfur trioxide and

Jan 1, 1968

By E. Furubayashi, T. Taoka, S. Takeuchi

Recrystallization textures developed from artificial nucleation around indentations were compared with spontaneously recrystallized textures in two rolled 3 pet Si-Fe single crystals with (111)[112] and (100) [011] orientations. Orientation of individual grains in some stages of their growth was also directly determined by a microetch-pit method. In both the crystals, the recrystallization texture was characteristic of each orientation regardless of any nucleation conditions, artificial or spontaneous, though artificially nucleated grains were more randomly oriented in finer stage. These results support the concept that the process of selection of growing grains controls the formation of the prejerred recrystallization texture. Discussion is given on the factors controlling the mobility of grain boundaries. Recrystallization textures are formed through a number of stages which are customarily called by the terms recovery, nucleation, and grain growth. Many experiments have been done to clarify the mech- anism of formation of recrystallization texture but no fully successful explanation has been proposed. The texture consists of oriented grains which nucleate at many sites of the deformed matrix and grow at the expense of the matrix during annealing. The current theories on the formation of recrystallization texture are based on the following two extreme hypotheses: 1) the oriented nucleation theory by Burgers et al.;1, 2 2) the oriented growth theory by Beck et al.3-5

Jan 1, 1968

By W. Bonfield

The microstrain characteristics of a polycrystal-line Cu 1.9 wt pet Be precipitation-hardening alloy have been determined for various conditions of aging. The friction stress remained constant for all the conditions investigated, whereas the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-8 in. per in.) and the three-stage stress-strain curve in the microstrain region were sensitive to changes in dislocation and precipitate distribution. Correlations between the measurements of microplasticity and electron-nzicroscope observations of substructure are considered. ALTHOUGH the macroscopic mechanical properties of Cu 1.5 to 2.0 wt pet Be precipitation-harden ing alloys were established' in some detail, there has been no previous investigation of the nature of microyield-ing in these alloys. This paper describes a high-sensitivity extensometer determination of microplasticity in polycrystalline Cu 1.9 wt pet Be, in which the friction stress, the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.), and the rate of strain hardening in the micro-strain region were measured for various conditions of precipitation. The structural changes accompanying aging in this alloy were examined using transmission electron microscopy, a study which differed from previous investigations as, in order to minimize grain boundary precipitation effects,' the solution-treated alloy was cold-rolled to 40 pet reduction prior to aging. Hence the extent of recovery and recrystalliza-tion, as well as the variation of precipitate morphology and distribution, were assessed. From these results possible correlations between the microstrain characteristics and the observed precipitate and dislocation structure are considered. EXPERIMENTAL PROCEDURE The material investigated was a commercial copper beryllium alloy (Berylco 25), which had a com- position of 1.9 wt pet Be and 0.2 wt pet Co. The alloy was solution-treated at 800°C, quenched in water, and then cold-rolled to 40 pct reduction. Tensile specimens of gage length 1 in. and rectangular cross section of 0.18 by 0.06 in. were prepared from the solution-treated, cold-rolled material and aged for 15 min, 2, 24, and 100 hr at 315°C and 24 hr at 425°C to produce a range of precipitate structure. The hardness values associated with these conditions are listed in Table I. It can be seen that a maximum value is obtained after 2 hr at 315oC, which decreases with continued time at temperature to a minimum after 24 hr at 425°C. For comparison some as-solution-treated specimens were also aged for 2 hr at 315°C. The specimens heat-treated to a given condition were examined in two ways. First, the nature and distribution of the precipitate and dislocation structure was characterized using transmission electron microscopy. Thin foils were obtained from the specimens by electrolytic polishing in a 30 pet nitric acid-alcohol solution at -20oC, and were examined in an RCA EMU 3 electron microscope. Second, the mi-croplastic behavior of the specimens was measured with a Tuckerman strain gage, using the load-unload technique previously described2, 3 to determine the friction stress, the microscopic yield stress, and the variation of plastic microstrain with stress. RESULTS 1) Structural Changes During Aging. a) Annealing Processes. The solution-treated, cold-rolled Cu 1.9 wt pet Be had an irregular dislocation-cell structure,

Jan 1, 1968

By H. G. Iverson

The effects of adding boron and boron plus carbon to electrorefined vanadium were evaluated with respect to mechanical properties at low temperatures and response to heat treatment. Grain size was significantly decreased with the addition of 0.05 percent boron, the decreases ranging from 30 percent at 800° C to 75 percent at 1,100° C. Increasing the boron content resulted in only a small increase in strength at room temperature, but at 77° K, boron contents of 0.005 to 0.076 percent increased the yield strength of vanadium over 50 percent, from 70,000 psi to 110,000 psi. When boron and carbon were present together, the individual grain-refining effects obtained with either element were retained. Approximately a twofold increase in strength was obtained by age-hardening the alloys containing both boron and carbon. Alloys with only boron additions did not age-harden.

Jan 1, 1968

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE use of galvanic cells for the determination of oxygen activities has spread rapidly since the suitability of calcia-stabilized zirconia as a solid electrolyte material was first demonstrated by Kiukkola and Wagner.' In many of these investigations:-7 including several at ARL, the free-energy changes for various oxidation-reduction reactions involving the oxides FexO, NiO, and Cu2O have been measured as a means of assuring that a cell apparatus is functioning properly. As a result, a large quantity of data pertinent to the calculation of the high-temperature standard free energy of formation (?GO) of these oxides has been accumulated. AGFexo has been carefully measured in many independent investigations, using a variety of techniques, and consequently is accurately known. chipmans has used this informa-

Jan 1, 1968

By John D. Corrick

A dilute sulfuric-acid leach was developed for extracting lead and copper from lead blast furnace mattes and the chemistry was defined. The possible application of Ferrobacillus ferrooxidans to the problem of salvaging lead and copper from blast furnace mattes was also investigated. Operating conditions were varied to determine their effect on the oxidation and hence extraction of lead and copper from the matte. Conditions varied were temperature, pH, reaction time, aeration in the slurry, and particle size of the matte. A set of optimum conditions were developed that resulted in maximum lead and copper sulfide oxidation. Tests employing these optimum conditions resulted in 82.3 percent of the lead and 98.7 percent of the copper being extracted by a dilute acid leach, while maximum lead and copper extracted using F. ferrooxidans was 69.8 percent of the lead and 78.4 percent of the copper. Tests conducted with a different sample of blast furnace matte indicated that the dilute acid leach might have wide application in extracting lead and copper from other such blast furnace mattes.

Jan 1, 1968

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,' regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal' was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult's law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By William S. Miska

The study is an economic evaluation of historical, current, and projected refractory uses in the iron and steel industry of the United States. The first part of the report presents a refractories classification and identifies principal trends in the refractories industry; such as, value and volume of shipments, prices of finished refractory products, the number of manufacturers and plants for refractories production and marketing. The main part of the report treats refractory use patterns and technologic developments affecting refractories usage in the iron and steel industry. Changes in use patterns in each furnace type, refractory, and installation costs and the future outlook for refractories in ironrnaking and steelmaking are covered. The last part of the report identifies the principal raw materials used in refractories production and treats trends in refractory raw material consumption. An appendix to the report contains historical time series graphs of shipments of refractory types used primarily by the iron and steel industry and principal refractory raw materials sold or used by producers. An equation of the line of best fit was calculated from the earliest to the latest year in each time series, usually 1950 to 1965; these were extrapolated in order to derive volume estimates for the year 1975.

Jan 1, 1968

By Hillary W. St. Clair

Reaction rate coefficients were determined from analyses of the effluent gas for the reduction of granular ferrous oxide to metallic iron by passing carbon monoxide through a packed bed of oxide at a controlled rate in the temperature range 1,000° to 1,300° C. Coefficients were determined by the comparison of observed analyses and calculated analyses using a mathematical model that takes into account the nonuniform composition of both the solid oxide and the gas. A method is also given for finding the value of the rate coefficient that best fits the observed data.

Jan 1, 1968

By N. A. Gjostein

The real and apparent dependence of the surface self-diffusion coefficient, Ds, of gold on crystallo-graphic orientation has been investigated by isolated scratch smoothing and grain boundary grooving experiments. No systematic variation of Ds with orientation was found along the [100] zone. In view of the experimental scatter in these results, however, only aniso-tropy ratios, p, greater than -1.3 would be detectable. Anomalously low values of Ds were found on the [0ll] and [110] zones when the diffusion direction lies along (the scratch or grain boundary groove is perpendicular to) these zones. By comparing these results with a previous y plot study of gold, it is hypothesized that this is not an intrinsic diffusivity effect, but rather it results from a decreased driving force for mass transfer at orientations where the y-plot curvature is negative and appreciable in magnitude relative to y. The characteristics of this type of anisotropy do not appear sEVERAL investigations1-7 have dealt with the anisotropy of the surface self-diffusion coefficient, Ds, of metals as measured by the decay of single or multiple to be in agreement with the hypothesis of fast diffusion along ledges in the surface structure. In certain cases the Fourier method of determining Ds, described in Paper I of this series9 was compared with the second moment analysis in order to determine whether or not the method of analysis affects the anisotropy ratio. While the type of analysis does influence the magnitude of the anisotropy ratio, this effect is not associated with the shape of the profile, but rather is connected with the iterative volume diffusion correction used in conjunction with the second moment analysis. It is further demonstrated that the volume diffusion correction can be too large by either method when the y-plot curvature effect is large. Certain orientations exhibit an unusual temperature dependence of Ds ; this is discussed in terms of the y-plot curvature effect and/or the influence of impurities on Ds . scratches in the surface. Depending on the system investigated, both large1"3'6'7 and small4'5 anisotropies in Ds have been found. Although adsorbed impurities undoubtedly play an important role in determining the magnitude of the anisotropy,8 there are other factors that can give rise to an apparent anisotropy in Ds, thus obscuring the true nature of an intrinsic anisotropy in

Jan 1, 1968