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By David P. Shoemaker, Clara Brink Shoemaker

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

Jan 1, 1968

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300' to 600°C in argon, it was sometimes found that a

Jan 1, 1962

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a') transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

By W. A. Tiller

The conventional techniques1 for determining the liquidus and solidus surfaces of an alloy system containing more than two components are extremely tedious to use and do not provide a complete picture of the equilibrium relations between solid and liquid alloys. These techniques are unable to yield "tie-line" information concerning solid and liquid phase equilibrium, a very important parameter in the solidification description of the liquid alloy and a very necessary parameter in the preparation of "zone-levelled" alloy crystals. The tie-line in a polycomponent system is analogous to the partition coefficient, k, in a binary system, it gives the composition of the solid, Cs, in equilibrium with a liquid of composition CL. That is, CS = kCL, where CL = [CO, c1,...Cn] denotes the concentrations of the n + 1 constituents, and k = [ko, kb ,...kon] denotes the gross partition coefficient for the elements between the two phases; thus, k is the tie-line in this system. To provide complete information concerning the two-phase equilibrium in a polycomponent system it is necessary to know both the liquidus surface and the gross partition coefficient. From these two the solidus surface is obtainable. The conventional techniques are unable to provide this information in other than a binary system so we must look elsewhere. In recent years considerable insight has been gained into the correct description of the liquid-solid transformation, 2,3 and controlled solidification experiments may now be designed to both facilitate and enhance equilibrium diagram studies. In the present paper consideration is given to two methods for obtaining the liquidus surface and the tie-lines in polycomponent systems. The methods to be described below deal with the solidification of an n + 1 constituent liquid alloy of initial composition [co, Co ,...Con], where the superscripts refer to the elements present and the Oth element is considered as the solvent in which the n solutes are dissolved. The general assumptions made in the treatment are the following: (i) the solid and the liquid at their interface are in equilibrium during the growth of the solid phase, (ii) there is no diffusion in the solid phase, and (iii) the liquid phase is completely mixed and is therefore homogeneous in concentration. METHOD I In this section a general experimental method will be described which, in principle, is capable of giving an exact description of the liquidus surface and tie-lines. Consider the unidirectional solidification of the liquid alloy specimens L cm in length (freezing either horizontally or vertically). Allow the sample to be frozen very slowly from one end, as indicated in Fig. 1, with complete mixing in the liquid, and then analyze the solid bar to determine its chemical constitution as a function of position, x, along the bar. Let Fig. 2 represent a possible distribution of the ith constituent along the bar. At the point x' the concentration of the ith constituent is C1/5(x'), and the average concentration of the rest of the bar between x' and L is given by C:(X' - L) where [ A(x) c1s(x)dx c1/s(x'-L) = f A(x) dx x * and A(X) is the cross-sectional area at x. In a similar manner. all the Cf(x' - L) may be determined. Thus, the gross artition coefficient k for liquid of composition [Cs(x - L),...Cs(X' - L)] is given by -ko= CUs')/Cos(x' - L)" k0 = csn{x')/cs(x'- L) During the freezing of a charge of length L, the liquid composition may vary over a wide segment of the phase diagram and the gross partition coefficient over this segment of the phase diagram may be determined from one, bar. Fig. 3 illustrates the magnitude of Cs(g)/C,' as a function of the fraction g of the bar which has Solidified.2 We can see that the concentration in the bar will vary over a range of about 15 wt pct for C,' = 10 wt pct and k0 = 0.5. It appears that 4 or 5 specimens would be adequate to study a simple binary eutectic phase diagram.

Jan 1, 1960

By E. Amott

A test is described in which the wellubility of porous rock is measured as a function of the displacement properties of the rock-water-oil system. Four displacemet operations are carried out: (I) sponlaneous displaceti?ent of water by oil, (2) forced displacement of water by oil oil in the same system using a centrifuging procetllrre, (3) spontaneous displacement of oil by water. and (4) forced displacment of oil by water. Ratios of the spontaneous displacement volumes to the total displucenlent volumes are used as wettability indicates. Cores having clean mineral surfaces (strongly preferentially water-wet) show displacement-by-waler ratios approaching 1.00 and displacement-by-oil ratios of zero. Cores which ([re. strongly preferentinlly oil-wet give the reverse resu1ts. Neutral wellability cores show zero values for both ratios Fresh cores from different oil reservoirs have shown wettabiltties in tlris te.st covering rrlti~ost 111e conlplrtt, range of thr: te.st. Notvever, nlo.s/ of tlle fresh California cores tested were slightly prcfere111icrlly wclter-\vet. The chrrnge.~ in coro u ('liabilities, as indicated hy this te.st, r~.sril/ing from various CO~P hanrlling procedures tt,ere oh.served. In sonie ca.sc,s /Ire ~,cttahilitio.c. of fresh cores were changell by drxi:~g or 11y e.x/rclct ing with iolcreiii~ or. dioxunc~; in o/h~r cases they were 1101 changed. Co~ltrrc/ of cort,.s ~.ith filtrc~t~c. from water-base rlrilling rilrrrls crlrc.sed littlc change in we/ /ahility ivhile contnct with filtrates frorii oil-hus~ ri1rlcl.s tlecrrascrl the prefcrerlcc, of the, cores for )I.NI Usitig thi,s test to ri.crl~lute n~r~ttubili~y, N .vt~ldy was iilarle of /lie correlmtio~i of wettability with wa/erfloocl nil recovery for orttcrop Ohio sand.stone and for Al~ln-tlunl. Resul/.v indicate thml no single correlatioti between these factors applies to different porous rock syste~n. It is thought that diflerences in pore gen~netry resrrlt in diflrrerrce.~ in this correlurio~z. INTRODUCTTON Most investigators who have reported on the wettahility of porous rock have described such rock as prcferentially water-wet or preferentially oil-wet. In some cases a third classification, neutral wettability. has been used. The efficiency of water floods in each of these wettability groups has been described in numerous publications. Several methods for characterizing porous rock wet tability more precisely have been reported,' " but it appears that because of one weakness or another. none of these has been generally accepted. Early in our studies in this field, it was found that the displacement efficiency of oil by water in a particular porous rock having a strong preference for water was quite different from that in a similar rock having only a moderate preference for water. Thus, there appeared to be a need for a practical, reasonably precise wet tability test. one which could classify porous rocks into 10 to 20 different groups rather than the two or three broad groups listed above. The test developed to meet this need is described in this paper. Also, changes in wettability, as indicated hy this test, resulting from various core handling procedures are discussed. Finally, data showing the corrclation of wettability with waterflood oil recovery for two different types of cores are presented and discussed. Some confusion has resulted from the failure of certain writers to define clearly some of the wettability terms they have used. Accordingly, the following commcnts concerning definitions are offered. The wc t ta-hility of a solid surface is the relative preference of that surface to be covered by one of the fluids under consideration. It is felt that this is the generally accepted definition. The fluids being considered must bc specified (or understood) before the term wettability has any significance. In the work reported here these fluids are water (3 per cent brine) and oil (kerosene). The term preferential wettability is sometimes used, but we think that the word preferential is redundant here and should not be used. Tn line with the definitions of Jennings', a preferentially oil-wet solid surface is regarded as a surface which will show an oil advancing contact angle less than 90" (measured through the oil) in the water-oil-solid system. Oil will spontaneously displace water, if both are at the same pressure, from such a surface. A preferentially water-wet surface is analogous. This is consistent with the wettability definition above. As Jennings has said, frequently the term oil-wet is used to mean the same thing as preferentially oil-wet. However, oil-wet also has been used occasionally referring to an oil-covered surface when the availability of water was limited. To avoid confusion from this source, we do not use the terms oil-wet and water-wet. DESCRIPTION OF WETTABTLITY TEST The following points were considered desirable in a wettability test for our purpose. 1. The test should be a displacement test resembling

Jan 1, 1967

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1&apos;2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900&apos; C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1&apos; and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods&apos;, " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.&apos; It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"&apos; on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday&apos;s law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday&apos;s law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday&apos;s law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,&apos; the values obtained were about a third those reported for a 5000 psi surface shear stress.&apos; RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.&apos; The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

Who&apos;s Who in Mineral Engineering - The 1978 Membership Directory of the Society of Mining Engineers of AIME

Jan 7, 1978

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.&apos;-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,&apos; and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By Charles Will Wright

DESPITE the war, the First Pan American Mining Congress, held in Santiago, Chile, Jan. 15-23, was attended by about 300 persons including the official delegates from sixteen of the American republics. The United States delegation consisted of Elmer Pehrson, of the U. S. Bureau of Mines; D. F. Hewett, of the U. S. Geological Survey; William H. Hobbs, of the Carnegie Foundation; and C. W. Wright, delegate of the Board of Economic Warfare and of the A.I.M.E. Mr. Wright was elected to head the delegation. Among the other members were Edward Steidle, of Pennsylvania State College and also an official A.I.M.E. delegate; John Huttl, of Engineering and Mining Journal; W. 0. Vanderburg, foreign mineral specialist from Lima, Peru; O. B. Hundley, of the American Cyanamid Co.; Horace Graham, of the Anglo-Chilean Nitrate Co.; and several officials and engineers from the Anaconda, Kennecott, and Bethlehem Steel companies&apos; mines in Chile.

Jan 1, 1942

By C. R. Taylor, John Chipman

THE study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8: I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. EXPERIMENTAL METHOD Furnace The furnace used in this investigation differed from previous designs and may be considered a fourth modification of the original rotating furnace. Its essential features are shown in Fig. I. The outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base C are alberene stone. The coil supports D are of "Formica," a material formed from phe-

Jan 1, 1942

By C.R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I&apos; The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By C. R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I&apos; The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965

By Y. L. Yao

THE NaT1-type compound may be considered as the penetration of two diamond lattices in such a way that a superstructure of the bcc lattice is formed. Examples of the NaT1-type compound of lithium are LiZn, LiCd, LiA1, LiIn, and LiGa. Except for LiZn and LiCd, each molecule of these equiatomic compounds contains a total of four valence electrons. In LiZn and LiCd it was suspected (for example, see Ref. 1) that the fourth electron was withdrawn from the 18-shell of zinc or cadmium. An incomplete 18-shell would have to show strong paramagnetism. In 1955 Klemm and Fricke2 determined the magnetic susceptibility of LiZn, LiCd, LiA1, and LiIn (also NaTl and NaIn). The molar susceptibility of the outer electrons of LiZn and LiCd was found to be not strongly but weakly positive; that of LiAl and LiIn not negative but weakly positive. Thus they questioned the hypothesis about LiZn and LiCd in particular and the description of the NaT1-type structure in general. However, they did not determine the magnetic susceptibility of LiGa. This note is to report results for all five compounds of lithium. The starting materials are 99.9 pct pure lithium sticks containing less than 0.005 pct Na. 99.9 pct Zn, 99.9 pct Cd, 99.99 pct Al, 99.999 pct In, and 99.999 pct Ga. Weighed amounts of two components were wrapped in tantalum foil and placed in a graphite crucible. It was found that the tantalum sheath minimized the vaporization losses of lithium during melting. The sheath was easily stripped from the alloy rod and the tantalum in the alloy was barely detectable (less than 0.01 wt pct). The melting was performed in a resistance furnace under an argon atmosphere. Alloy specimens were annealed for 1 hr at 400°C in vacuum. The magnetic susceptibility at room temperature was determined by the Faraday Method, using the procedures previously described.&apos; The results are shown in Table I. The interpolated values at 50 at. pct of Li and the average values at 48 to 52 at. pct of Li at 20°C determined by Klemm and Fricke2 are also shown. It is seen that the present value for LiZn and LiCd is slightly more positive but the present value for LiAl and LiIn is slightly less positive than their corresponding values. Also, it is noted there is an abrupt decrease of susceptibility of LiAl from 51.2 to 52.5 at. pct of Li. Klemm and Fricke2 found that the total susceptibility of LiZn, LiCd, LiA1, and LiIn is almost independent of temperature. slater4 gave a working expression for the diamagnetism of the atomic core as follows:

Jan 1, 1964

By Leonard B. Lipson

Boyer, Morgan and Muskat,&apos; with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,&apos; have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/&apos;E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951