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By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By J. Richter, D. Schulze

J. Richter and D. Schulze (Deutschen Akademie der Wissenschafte zu Berlin)—Introduction. In a recent paper R. G. Garlick and H. B. Probst reported on experimental results of investigations of room-temperature slip in zone-melted tungsten single crystals.17 In the paper it was pointed out that slip lines could be detected with an optical microscope only after about 10 pet plastic strain of the crystal. In our investigations we could observe slip lines in tungsten single crystals of defined orientations already with an elongation of 0.02 to 0.03 pet.18"9 Experimental Technique and Results. The tungsten single crystals were produced from 4 to 5 mm sintered rods* as starting material by electron- beam zone melting. With single-zone-pass melting a speed of 0.5 mm per min was used, while three-pass melting could be handled at a speed of 3 mm per min. Crystal axis orientations were located in the shaded area of the stereographic triangle, see Fig. 6. Orientation 1 is located at about 18 deg and orientation 2 at about 5 deg on the great circle from [011] to [ill]. This corresponds approximately to the orientations P and M referred to by Garlick and Probst. Our single crystals had a length of about 70 mm and were profiled solely by electrolytic means, leaving grip ends at both ends of the crystals. Between the latter, a cylindrical crystal of 45 to 50 mm length and about 2.4 mm diam was obtained. The crystals were deformed at room temperature in a commercial tensile-testing machine to obtain a strain of 0.02 to 5 pet. The average strain rate e = eP/t for all tensile tests amounted to approximately 10 -6 to 10-5 per sec, with ep representing plastic strain and t the duration of applied stress. In Fig. 7 a crystal is shown elongated by 0.03 pet. The picture was obtained by means of an optical microscope. Figs. 8 and 9 give electron-microscopic pictures of slip lines of crystals elongated by 0.07 and 1.1 pet, respectively. For crystals with the orientation 1, see Fig. 6, only the two main slip systems (101)[111] and (110)[111] were found. With the crystals of group 2 the two main slip systems are again evident, with

Jan 1, 1965

By P. S. Rudman

The allotropic volume changes of the ,metallic elements are reviezoed with the conclusion that in general atomic volume is conserved to better than 1 pct in such transformations. A table of the atomic volumes of the metallic elements is given and its use in considering the size factor in alloys is discussed. The importance of the concept of atomic-size factor, due to Hume-Rothery and coworkers,' is firmly established. Most attempts at quantitative formulations of this concept have employed the atomic radius (half some interatomic distance) as the measure of size and innumerable tables of such radii exist. This is probably, however, an unfortunate choice of parameter. Firstly, discussion in terms of interatomic distances requires a knowledge of the crystal structure. While this is known, except for a few cases, for the elemental structures, there are still many undetermined alloy structures. Secondly, except for the simpler structures, face-centered cubic (Al),* body-centered cubic (A2),* and hexagonal-close-packed (A3).* with ideal axial ratio, there is no unique in- teratomic distance, an m y decision must be made as to which distance, or which average of the distances, should be used. However, the most important point is that for metals the dominant bonding parameter can generally be expected to be atomic volume and not interatomic distance. This is perhaps most explicitly stated in the Wigner-Seitz cellular method.' In this approximation, cellular polyhedra of atomic volume v are replaced by spheres of radius Y,: 4/3 ?rs3 = v. That is, there is no reference to the interatomic distances. If atomic volume is in fact the dominant parameter, then in allotropic transformations we might expect to find atomic volume approximately conserved. For example, in the A1 ? A2 transformation we would thus have

Jan 1, 1965

By Dell P. Williams, Howard G. Nelson

The tensile behavior of magnesium single crystals at a temperature of 26º ± 2ºC was investigated at varying pressure levels from 760 to 8 X 10-8 tow. For crystals deformed at a constant linear strain rate of 0.061 min-1. there was no apparent effect of the vacuum environment down to 10-8 torr. However, from a vacuum of 10-5 torr down to the lowest pressure attained (8 x 10-8 tor,), the effect of the vacuum environment was to increase the strain at the end of the first linear (or easy-glide) stage and to decrease the slope of this stage; the magnitude of this effect was found to be dependent on pressure. The slope of the second linear stage was also decreased at the lower pressure levels; however, this effect appears to be caused primarity by the vacuum effect on the first linear stage. The magnitude of the vacuum-environmrnt effect was also found to be dependent upon strain rate. The reduction in flow stress at 5 x 10-8 torr, as compared to the stress in air, was obserced to be about 10 pct for a strain rate of 0.0250 min-' and 70 pct for a strain rate of 0.67 min-1. No systematic effect of pressure on the critical resolvled shear stress was observed. The data interpreted in terms of a modified form of Mott's work-hardening mechanism for hexagonal metals. It has long been known that surface conditions influence the mechanical behavior of materials. Roscoe 1 demonstrated the importance of surface conditions on mechanical behavior by testing cadmium crystals with oxide layers. He found that the "apparent" critical resolved shear stress for cadmium was increased approximately 2.5 times by the presence of an oxide layer 1000 atoms thick. The magnitude of this effect was dependent on film thickness with crystals having films less than 20 atoms thick still showing a definite increase. This observed strengthening could not be attributed to any strength of the oxide film because of 1) the thinness of the films and 2) an observed increase in the flow stress as deformation proceeded. Harper and cottrel12 obtained similar results on zinc crystals which had been etched and steamed to give artificially thick oxide films. However, in the course of this study, they also carefully examined the very early stages of plastic flow for zinc crystals which in one case had been electrolytically polished and in the other had been lightly etched to produce a thin film. They then found that the critical resolved shear stress for both surface treatments of the crystals was actually identical but that the etched crystal exhibited a much more rapid initial hardening rate. This had not been noted previously. This result indicated that, in fact, the film caused an increase in the stress for continuation of slip, rather than for the initiation of slip. Lipsett and King3 investigated the effect of evaporated gold films on the plastic behavior of cadmium single crystals. For large angles (=75 deg) between the specimen axis and the normal to the slip plane, they found that the stress-strain curve of the coated specimen always lies above that for a clean specimen. The shear strain at the end of the first linear stage was greater in clean specimens than in coated specimens and the slope of the second linear stage was

Jan 1, 1965

By D. K. Atwood

Experiments resulted in a satisfactory laboratory method for restoring permeability to clay-containing cores damaged by fresh water. Clay contents of a number of field cores were measured, and permeabilities of plugs from these same cores were then deliberately reduced with fresh water. This damage is attributed to swollen and dispersed clays occupying the pore space. After damaging, a number of experiments were performed to meaJure the amount of damage and to establish some means by which permeability could be restored. The experiments included flooding the damaged cores with water-miscible fluids such as salt water, acetone, isopropyl alcohol and ethanol. Permeability was not successfully restored in these experiments. However, part of the damage was repaired by flooding with oil; when water was removed by distillation in the presence of immiscible fluids such as air or toluene, permeability was completely restored. This evidence suggested that swollen and dispersed clays could be collapsed to their original volume by strong interfacial and capillary forces. It was further postulated that the required forces could be generated by flooding the damaged cores with a solvent partially miscible with water. The flooding experiments were repeated using n-hex-an01 as the partially miscible solvent. Permeability was restored to five of six damaged cores and substantially increased in the sixth. A large fraction of the restored permeability was retained even after water saturation was raised to its original value with 12 per cent salt water. INTRODUCTION Sharp reductions in permeability often occur when relatively fresh water contacts clay-containing formations during drilling and workover operations. These permeability losses are caused by removing inorganic ions from the environment surrounding the clay, and consequent swelling and/or dispersion of clay minerals into the available pore space.' This phenomenon is generally termed clay damage, fresh-water damage, or simply formation damage; it causes large losses in current revenue by preventing oil wells from making their allowable production. Attempts to repair the damage and restore permeability by flowing salt water solutions or brines through clay-damaged cores containing montmorillonite have been unsuccessful.' This irreversibility is thought to result from formation of brush-heap, or edge-to-face, structures when the dispersed clay is flocculated. The brush-heap structures occupy much more space than the close packed domains present before damage.' One solution of the problem is to destroy the clay-water brush-heap and thus restore permeability. Because no satisfactory method existed for restoring permeability to clay-containing formations damaged by fresh water, the work described in this paper was under taken. The laboratory experiments generally consisted of deliberately damaging fresh cores containing clay and then attempting to repair this damage by various means. Results indicate that generating strong interfacial forces within the pore space of damaged cores collapses the clay brush-heap and restores permeability. These forces are most conveniently generated by flowing partially water-miscible solvents, such as n-hexanol, through a core. THEORY OF THE DAMAGE PROCESS The most common clay mineral groups known to cause permeability damage to formations are the mont-morillonites, kaolins, chlorites and illites. These clays are constructed of particles which can adsorb water on their surfaces and edges and, in the case of montmorillonite, between layers of the basic particle itself. This adsorption increases as water salinity decreases. At low salinities the particles disperse into the aqueous phase. When the clays present in the formation are kaolin, chlorite and illite, dispersion accounts completely for permeability damage to porous media. However, unlike the other clays, montmorillonite particles can imbibe water and adsorb ions between layers of sub-particles, or platelets. These platelets have net negative charges on their faces and are held together by exchangeable (or removable) cations such as Na and Ca decrease in ion concentration (salinity) in the fluid surrounding a particle causes migration of water into the clay layers and disperses the basic particle, while diffusion removes the original exchangeable ions from between the platelets. Once these ions are removed, the facing negative platelets repel each other, causing the montmorillonite to swell until, for all practical purposes, the individual platelets are dispersed. For this reason, fresh-water* damage is much more severe in sands containing montmorillonite than it is in sands containing other clays. Many investigators have shown that even trace amounts of montmorillonite can be responsible for marked reduction in the permeability of reservoir sands in the presence of fresh water." ." Monaghan and others have shown that fresh-water damage in montmorillonite-containing cores cannot be

Jan 1, 1965

By W. Hume-Rothery

IN recent interesting papers,1,2 Bardos et al. have described ternary Laves phases of the type A2(BsSi) and A4(B5Si3) where A = titanium vanadium, niobium, and so forth, and B = manganese, iron, cobalt, or nickel; other more complex formulae have also been established. In these phases, silicon plays the part of the smaller B atom of a Laves phase AB2, and the interatomic distances show that the effec- tive silicon radii lie between 1.16 and 1.21Å, and are thus very much smaller than the metallic radius of silicon for CN = 12. It does not seem to have been pointed out that these small atomic radii are almost the sape as the normal covalent radius of silicon (1.174Å). If, therefore, silicon acts as an acceptor of electrons as suggested by Bardos et al.,1 it appears to do so, not by the building up of a negatively charged silicon ion which would be large, but by the formation of what are very nearly or may be actually normal covalent bonds. Since a covalent bond contains two electrons, its formation would reduce the number of electrons available for bonding in other parts of the structure, and in this way the effect of silicon in stabilizing the o phase at high electron concentrations might be understood.

Jan 1, 1965

Jan 1, 1965

By R. Littlewood

The concepts of "redox potential" and "oxide-ion activity" are suggested as measures of the fundamental slag properties of interest to the extraction metallurgist. Thermodynamic data for single oxides are presented graphically in these terms and a method of expressing desulfurization of steel in electrochemical terms is indicated. The application of the theovy to mixtures of oxides (slags) is discussed and the redox potential is shown to provide a link between all the redox equilibria in a slag-metal system. In particular, the redox potential of the slag, its basicity, and the oxygen partial It is now generally recognized that slags are mixtures of polymeric anions of silicates, aluminates, phosphates, and so forth, neutralized by cations. However, conventional thermodynamic treatments of slags have almost always been in terms of activities of the pure component oxides (e.g., SiO,, CaO, A1203, and so forth), which are known not to exist as such in slags. While this type of empirical treatment is perfectly acceptable and provides a rigorous and self-consistent way of considering thermodynamic properties, it can give little guide to the structure of slags, since its very nature ig- pressure are closely connected. Direct deternzination of these by electrode-potential measurements is possible. Literature calculations of ion activities in the system Ca0 -Fe0-SiO,/molten iron are used to evaluate redox potentials, which are shown to correlate with data on sulfur partition in the system. In addition to its application to equilibrium conditions, an electrochenzical approach to slag-metal reactions might provide a basis for new methods of studying the kinetics of these reactions and for plant-control instruments in the pyrometallurgical industries. nores such complications. Recently, the thermodynamic properties of some slags have been successfully interpreted in terms of activities of anions of varying degrees of complexity. (While these have been successful curve-fitting exercises, there is no direct implication that the anions used in the models are necessarily the ones which actually exist in slags.) The success of these ionic thermodynamic treatments is encouraging but a complete picture of slag structure is still a long way off. What is needed is a complete knowledge of the values of stability constants for all reactions in slags of the type:

Jan 1, 1965

By T. S. Lundy, C. J. McHargue

HE diffusion rate of v48 in single crystals of bee vanadium has been determined at temperatures from 1002° to 1888°C. Standard techniques of lathe sectioning were used for specimens annealed above 1500°C while sectioning by grinding was used for specimens annealed at lower temperatures. As will be seen, the lower-temperature data is enhanced on an Arrhenius-type plot relative to values expected by extrapolation of the high-temperature data. Single crystals were obtained from Linde Co. In Table I the analysis supplied by the vendor is compared with an analysis at Oak Ridge National Laboratory of a sample after a diffusion anneal. The isotope v4' was prepared by the Isotopes Division of Oak Ridge National Laboratory. Proton bombardment of a titanium target in the 86-Inch ORNL Cyclotron was followed by a carrier-free chemical separation. Nineteen specimens, 1/2 in. diam and 3/8 in. long, were cut from the as-received vanadium single crystals. Each specimen was machined with the flat face perpendicular to the longitudinal axis. Specimens were polished through 1/0 emery paper and were etched with 25 pct HF-10 pct H2SO4-10 pct HNO3-55 pct H2O. The polishing and etching steps were repeated until a satisfactory surface finish was achieved. The isotope was electroplated onto the specimens from a neutral solution. Counting rates of the deposited layers were approximately 100 counts per sec. At temperatures above 1200°C specimens were annealed in a tantalum resistance furnace under an argon atmosphere. Temperatures were measured with a Pyro micro-optical pyrometer and a Pt-Pt 10 pct Rh thermocouple. At lower temperatures the specimens were sealed in evacuated quartz ampoules and annealed in Kanthal wire-wound horizontal tube furnaces. A severe reaction occurred at 1200°C between the quartz and the vanadium. This

Jan 1, 1965

By J. P. Hirth, C. S. Hartley

A simple graphical technique is presented for rapidly determining the ratio of resolved shear stress on slip systems in single crystals to the applied stress (Schmid factor) for various simple states of stress. Master plots are presented which, when used in conjunction with an appropriate stereo-graphic projection, allow one to determine the Schmid factor for all slip systems in a crystal of given orientation. It is shown that one such plot suffices for simple tension or compression, flex-ural bending, and biaxial compression, while a combination of two different plots must be used for torsion and simple shear. STUDIES of the deformation behavior of single crystals are most valuable when the applied stresses are resolved onto the various slip systems of the crystal. A careful study of the available slip systems and proper selection of the state of stress used and the specimen orientation can then yield quantitative information about the probability of specific dislocation reactions, the strength of barriers to plastic flow, and the mechanisms of yielding and flow in general. It is the purpose of this work to analyze some common states of stress used in deformation studies and to present a simplified way of determining for these cases the ratio of the resolved shear stress on the slip systems to the applied stress (Schmid factor). I) CALCULATIONS We first define two orthogonal coordinate systems: one based on the specimen geometry (a right circular cylinder of radius, R, is considered here) and one based on the particular slip system of interest. The unit vectors and angles specifying the two coordinate systems and the relationship between them are listed in Table I. The relationships among the various angles and unit vectors are shown on a stereographic projection in Fig. 1. The transformation matrix between the (XI X2 X3) and (x'1 x'2 x'3) system is x1 x2 x3 X'1 a11 al2 a13 x'2 a21 a22 a23 x'9 a31 a32 a33 where in this case the direction cosines aij are given by a11 a12 a13 aij = a21 a22 a23 a31 a32 a33 sin 0 cos F cos 0 sin F cos 9 = -cos 0 cos F sin 0 sin F sin 6 [1] 0 -sin F cos (p In terms of Eq. [I.], the stresses sij, referred to the slip system, are determined from oij, referred to the specimen axes, by1,2

Jan 1, 1965

By A. Hellawell

Binary alloys of compositions intermediate between solid-solubility limits and eutectic compositions have been completely separated into primary phases and eutectic by freezing unidirec-tionally at very slow rates (10-6 to 10-5 cm per sec). The alloys examined were Pb-1 wt pct Ag, Al-20 wt pct Cu, and Al-42 wt pct Cu. The compositions and proportions were close to those expected from the phase diagrams and provided information about the solid/liquid interface at certain free zing rates. DURING the directional freezing of an alloy the solute distribution is controlled by the efficiency of mixing in the liquid,'" whereas diffusion in the solid state is of negligible importance. It is known3 that mixing by convection is very efficient, but complete segregation is only achieved at very slow freezing rates4-6 or with forced stirring in the liquid. ' Yue9 and Yue and clark10 have previously illus- trated partial separation of primary phases in alloys close to eutectic compositions. In the present work, taking binary alloys of compositions intermediate between the limits of solid solubility and eutectic compositions, it has been possible to achieve complete separation of the primary phases by directional freezing at very slow rates. METHODS AND RESULTS The alloys concerned were Pb-1 wt pct Ag, A1-20 wt pct Cu, and A1-42 wt pct Cu. As may be seen from the relevant diagrams,11 these alloys should segregate into approximately equal proportions of primary solid solutions and alloy of eutectic compositions. Specimens, -12 cm long and 1 cm wide, were frozen in horizontal tubes by withdrawal from a furnace. The lead alloy, prepared from materials of 99.999 pct purity, was sealed into evacuated Pyrex tubes and the aluminum alloy of similar purity contained in graphite boats under vacuum. The molten alloys were seeded with some 3 cm of solid to prevent irregular initial freezing rates and the last portions to freeze were ignored. At the slow freezing

Jan 1, 1965

By Herbert A. Wendel

Reaching the miner with safety education" is R the ultimate goal, the main objective, of every safety program in the mining industry. If we can get safety education to every worker, and it is properly learned, enforced and obeyed, we should eliminate at least 85% of all potential accidents. We should then have very few accidents as a result of unsafe behavior, which, in turn, would allow us to concentrate most of our future efforts on preventing the types of accidents which are caused by faulty or defective machinery, equipment, tools and materials. An uninformed or uninitiated person would think that it should be a rather simple process to reach the miner with a safety education. Theoretically he would be right because here we get involved in a matter of semantics. When we say "reaching the miner with safety education" we actually mean that this education must also be accepted and learned by the miner; we intend to mean that safety must be observed and followed at all times. But in order to realize our complete meaning of the phrase, we must find the solution for a number of problems and obstacles which are well known to management and safety personnel.

Jan 1, 1965

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By G. R. Kotler, W. A. Tiller, H. V. Ashcom, S. O&apos, Hara, W. C. Johnston

The grain-refinement effect of electromagnetic stirring of Sn-Pb alloys during solidification is investigated at higher field strength and in larger-sized samples. It is found that the grain-refining effect is due to a crystal multiplication phenomenon rather than a nucleation phenomenon. The effect increases with sample size for a fixed field strength and a fixed supercooling bath temperatures. The effect in other alloys was investigated. IN a recent publication1 it was reported that significant grain refinement could be produced during the solidification of a supercooled melt of Sn-Pb alloy when a critical degree of electromagnetic stirring was present in the melt. Thus, for a particular supercooling, AT, a critical magnetic field, Hc, existed at which the number of grains per unit volume, n, increased rather abruptly by a factor of 103 to 104 as the field, H, was increased by a small amount. It was further found that the undercooling at which the melt spontaneously nucleated, ?Tn, was independent of the magnetic field. These authors matched their experimental results against the qualitative expectations of existing theories and found each theory somewhat unsatisfactory. One important question that was not answered in this previous work was "should the effect be classed as a nucleation phenomenon or as a crystal-multiplication phenomenon?" Other valid questions that need answering are: i) do higher magnetic field strengths alter the nature of the results?; ii) what is the effect of higher lead content in the alloy?; iii) what changes occur when one extends the experiments to larger-diameter samples?; and iv) is this a universal effect applicable to the grain refinement of all materials? The present work directs its attention to answering these five questions. The

Jan 1, 1965

By H. L. B. Gould, Jr. Wenny D. H.

TO date there has been but limited interest in alloys of 80 to 95 pct Co and Fe with or without other additions. In 1932, S. R. Williams' reported practically zero magnetostriction for the 90 pct Co-10 pct Fe alloy. This same composition was used for pole pieces to control the magnetic field in magnetrons operating at high temperatures.' In 1947, a 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn composition was investigated3 for use in ballast lamps because of its high temperature coefficient of resistance. Recently, as part of a survey of ductile and malleable magnetic alloys capable of being processed to thin gages for possible applications in memory devices, the high Co-Fe alloys have been re-examined to determine their fabricating and magnetic characteristics. Alloys from 80 up to 95 pct Co and Fe with and without additions such as vanadium were prepared. In general these all had excellent ductility and malleability. Wire was drawn to thin gages without difficulty and fine hard-drawn wires flattened to 2) The phenomenon may have potential in estimating the carbon content of molybdenum. A given solution-treating temperature and cooling rate could perhaps be calibrated so that the area fraction of surface covered by carbide could be interpreted in terms of carbon concentration. By segregating to the surface, a big "magnification" of the carbon content is obtained, which should make the method cheap, direct, and sensitive and, therefore, perhaps of interest to the molybdenum industry. This work was conducted at Battelle Memorial Institute. Financial support by the Aeronautical Systems Division, United States Air Force, under Contract No. AF 33(657)-7376, is gratefully acknowledged, and the writer is thankful for the experimental assistance of Miss Marjorie Cantin. ribbon without splitting. Similarly, strip was cold-rolled as much as 99.75 pct reduction to a 0.25 mil thickness without intermediate anneals. Samples of round and flat wire and foil, in the severely cold-worked and annealed states, were checked for magnetic characteristics. The alloys exhibited widely divergent magnetic characteristics depending on the processing and heat-treating procedures used in preparing the samples. Direct-current hysteresis loops showing the different magnetic characteristics of 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn alloys are shown in Figs. 1 to 8 inclusive, while Figs. 9 and 10 show the loops for an alloy of 82 pct Co, 11.75 pct Fe, 5.6 pct V, and 0.65 pct Mn. Figs. 1 and 2 show the high remanence and exceedingly square-loop characteristics of the hard-drawn wire and ribbon roll flattened therefrom. With the change in processing from roll flattening to flattening by drawing through flat diamond dies the resultant change in texture is accompanied by the drastic change in the shape of the loop as shown in Fig. 3. This skewed loop on annealing reverts to a more normal loop as shown in Fig. 8. The most unique loops are obtained with flat rolled strip. These are shown in Figs. 4 and 5. In the case of the hard-rolled material, Fig. 4, there is little change in induction until the magnetizing force reaches 50 oe. From 50 to 60 oe there is a sharp increase in induction to over 15,000 gauss, which for all practical purposes is saturation. The induction remains at a constant value while the magnetizing force decreases to 40 oe. At this point the

Jan 1, 1965

By B. E. Warren

Jan 1, 1965

By B. A. Kulp, R. R. Reeber

Lattice parameters for the wurtzite form of' CdS mere measured by powder X-ray diffraction techniques over the temperature range 26° to 1000 K'. A negative thermal -expansion coefficient was determined parallel and perpendicular to the c axis below 13.5°K. Near 808°K, the curves of the a, parameter, the differential thermal expansion, and the resistivitv vs absolute temperature exhibited a reversible discontinuity. j\. direct determination of the lattice parameters of CdS over an extended temperature range is of particular use in interpretation of the effects of high pressure on the band structure of semiconductor materials. For example, Langer' has studied the effects of pressure on the absorption edge of CdS from 77°K to room temperature. In order to properly interpret his results it is necessary to know the change in lattice constants as a function of temperature for the wurtzite, zincblende, and rocksalt2 modifications of this material. Thermal-expansion measurements for CdS, wurtzite phase, have previously been determined over a limited temperature range.s74'5 The zincblende phases, of other compounds with similar bonding, have been investigated by Novikova et a! .'' Previous thermal-expansion measurements for metals with hexagonal symmetry have for the most part used bulk sample techniques for low-temperature result. Most X-ray measurements at low temperature have been on materials with cubic symmetry.'jQ The use of X-ray powder-diffraction techniques offers a convenient and accurate method of measurement over a wide temperature range. The X-ray method, besides measuring unit cell size, also provides information about change in structure type and the nature of some of the stacking defects present. I) EXPERIMENTAL PROCEDURE The thermal expansion was measured by X-ray powder-diffraction techniques. Lattice parameters for the range 300" to 1000°K were determined in a 19-cm Unicam camera. From 26" to 300°K a 34-cm back-reflection camera with the Van Arkel" film arrangement was used. The sample was bonded to a copper cold finger below a helium, hydrogen, nitrogen, oxygen, dry ice, or ice brine bath in a metal cryistat. che inner bath was surrounded by another one for radiation shielding. Nitrogen was used in this outer bath for the very low-temperature runs while dry ice and acetone was used for the 195°K point. CuKa X-rays, filtered with a nickel foil, entered the cryostat through a 0.001-in.-thick aluminum window. During a typical 9-hr exposure the sample was continuously rotated through a 30-deg arc. Heat losses from the sample holder limited the minimum temperature attained to 26°K with helium in the inner dewar. Temperature calibration between 25" and 125°K was determined with an Allen Bradley 300-ohm carbon resistor. The resistor was attached to the back of the copper finger with a thin layer of silicone grease. Liquid He, HZ, N2, and O2 baths were used to calibrate the resistor. Temperature variation is estimated to be *2"K with a slightly higher uncertainty at room temperature and 264°K. The thermal expansion of high-purity germanium from 373" to 900°K was measured as a calibration for the Unicam camera. This value was compared with the known value1' for the thermal expansion. A discontinuity in the thermal-expansion coefficient of the CdS a, parameter was observed. Similar discontinuities in the resistivity and differential thermal analysis at the same absolute temperature indicate that the temperature error is *5°K in the temperature range above 500°K. Temperature errors in the Unicam camera below 500°K are appreciably higher due to large gradients in the resistance furnace. II) SAMPLE PREPARATION The CdS was Eagle Picher ultrapure grade. The crystallite size range of the as-received powder

Jan 1, 1965

By James A. Roberson

THE mechanical behavior of molybdenum has become a matter of considerable interest in recent years because it has a reasonably high strength at high temperatures. Various aspects of its fatigue behavior have been investigated previously,1-3 and the results can be summarized as follows. Recrys-tallized molybdenum exhibits a fatigue limit which decreases continuously with increasing temperature. The ratio of fatigue-limit stress to ultimate tensile stress is high (0.6 to 0.8) and reasonably constant. The present work was undertaken to determine the effect of variations in environment on the fatigue of molybdenum stressed in fully reversed axial tension compression. In order to provide a basis to which these data could be compared, a complementary series of fatigue tests were made in vacuum. All of the specimens used were made from one mill lot of unalloyed molybdenum which had been vacuum-arc melted, worked down to 1-in.-diam bar, re-crystallized, then warm-worked to 5/8 in. diam. The interstitial content by weight was as follows: C—0.022 pet, 02-0.0026 pet, Hz-0.0001 pet, and N20.0002 pct. The average grain diameter in the transverse direction was about 0.035 mm, and the average grain length was about 0.15 mm. Typical tensile-test data are shown in Table I. None of the specimens tested exhibited an upper yield point.

Jan 1, 1965

By R. E. Caffrey, S. K. Tung

This paper reports some of tile results obtained from the vapor-phase reaction of a volatile metal halide with a hydrogen and carbon dioxide mixture in an epitaxial-deposition chamber. Tile oxides deposited were silicon di oxide, aluminum oxide, mix-12tves of silicon di oxide and aluminum oxide, and titanium oxide. Tile deposited silicon di oxide was transparent and amorphous and had a density and index of refraction similar to that of thermally grown silica. The vote of etching was determined. The thickness uniformily of the oxide was found to he related to the aerodynamics of the system employed for deposition. A clear silicon di oxide layer was found to be dependent upon the quality of the surface prior- to aside deposition. The process parameters affecting the vale 0f deposition were studied. The deposited aluminum oxide was transparent, holy-cl-ysttrlliile, and possessed remarkable resistance to hydrofluoric acids. By measurements it has been shown that the deposited aluminum oxide is both insulating and continuous. ThE cleanness of an epitaxial silicon surface both immediately after growth and during device processing is thought to be one of the major factors contributing to the electrical properties of a final device. The advantage of protecting an epitaxial silicon wafer surface with an oxide grown immediately following epitaxial deposition is obvious. The successive growth of silicon and silicon diox- ide in epitaxial apparatus was studied by Steinmaier and loem.' They formed silicon dioxide films on a silicon substrate by adding water vapor to the silicon tetrachloride-hydrogen mixture in an epitaxial system. They also showed that, when a gaseous mixture of carbon dioxide and hydrogen is injected, water is formed only at elevated temperatures. Thus the reaction of water vapor and silicon tetra-: chloride will be limited to a relatively small reaction zone near the substrate. This paper reports some results of oxide films obtained from a vapor-phase reaction of a volatile metal halide with a hydrogen and carbon dioxide mixture in an epitaxial-deposition chamber. EXPERIMENTAL APPARATUS The system employed for the oxide deposition is a modification of a vertical system used to produce high-resistivity silicon layers by the hydrogen reduction of silicon tetrachloride.' The modification shown schematically in Fig. 1 consisted of an additional carbon dioxide gas stream which entered the reaction chamber with a hydrogen stream saturated with metal halide vapor and a diluting hydrogen stream. Silicon dioxide layers made from a mixture of silicon tetrachloride, hydrogen, and carbon dioxide gases will be discussed first. EXPERIMENTAL RESULTS 1) Factors Affecting the Rate of Oxidation. An epitaxial silicon layer was deposited by the hydrogen reduction of silicon tetrachloride on an n-type,

Jan 1, 1965

By Kenneth N. Weaver

Portland cement can be made from relatively abundant industrial minerals and rocks, and this may explain why cement producers placed little emphasis on geology during the early days of the industry. After World War II, however, the industry began to recognize the need for geological exploration, and some of the larger companies began to build a permanent geological staff. This development had its roots in the following factors: Rapid expansion of the industry; closing of many cement plants due to inadequate raw materials; necessity for upgrading the quality of portland cement; and the increasingly large capital investment required to build new cement plants, which in turn, required a higher degree of accuracy in reserve calculations. Whereas the geologist's function during the active expansion of capacity was primarily in exploration, one of his major functions today is the development of existing reserves.

Jan 1, 1965