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By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

By T. P. Meloy

Recently, Gilvarry1 has criticized the Gaudin-Meloy2 derivation of the size distribution equation for impact grinding. The criticism states that as the derivation stands it is good for only a long, thin wire being fractured. This paper contains a second derivation in reply to the criticism. Consider a homogeneous solid particle. This particle is broken into fragments by impact. It is assumed that the material resembles galena and that the particles were broken into chunky parallelepipedes which may be treated as cubes. The fragments are now reassembled — as seen in Fig. 1 — and a line is passed through the fractured solid perpendicular to one of its faces. For simplicity, the length of the line segment in the cube is considered to be 1. Fig. 2 represents the line segment in the cube showing the locations of the crack surfaces cutting the line and one point, P, chosen at random on it. The question arises as to what is the probability of the point, P,

Jan 1, 1963

By F. A. Crossley

The additions: o, Sn, Zr, Cb, Mo, and V were studied for their effects on the a/a + Ti3A1 boundary of Ti-A1 base ternary alloys. These additions were chosen because of their importance to commercial titanium alloy practice—oxygen as the major impurity (in terms of influence on mechanical properties) and the others as major alloying additions. The composition and temperature ranges of investigation varied according to the system as shown in Table I. The principal means of investigation was light-microscopy. The basis of the ternary studies was the recently determined titanium-rich end of the Ti-A1 system.' MATERIALS, METHODS, AND PROCEDURES Ingots were prepared in 15 g size for all alloys except those of the Ti-Al-Mo and Ti-A1-V systems which were prepared in 20 g size. These alloys were prepared from high-purity, electrolytically refined titanium obtained from the Bureau of Mines, Boulder City Metallurgical Laboratory, Boulder City, Col., and Chicago Development Corp., Riverdale, Md., for the 15 g and 20 g ingots, respectively. The alloying additions were obtained from commercial sources, and were at least of 99.9 pct purity, except the V-15 wt pct A1 master alloy for vanadium additions. This alloy was of 98.2 pct purity; the major impurities were 0.37 wt pct Fe and 0.38 wt pct Si. The ingots were prepared by multiple melting in a nonconsum-able-electrode arc furnace. The ingots were covered with Markal coating "CR-T22" (Markal Co., Chicago) to protect them from scaling. Markal coating is applied as a slurry of solids in a volatile carrier liquid. The coated article is air dried. Upon heating to the hot working temperature the coating fuses to form a glassy, protective film. The ingots were heated to 1000°C and rolled to 0.16 in. thickness, reheating after each pass. The glassy film was removed by sand blasting. Ten mils were removed from all surfaces by grinding and/or pickling (3 pct HF, 30 pct HN03, balance water). Grinding was always followed by pickling to remove traces of the grindmg medium. Hydrogen removal was accomplished by vacuum annealing at 1000°C for 2 hr to a final pressure of about 0.02 µ Hg. This was followed by annealing in evacuated Vycor bulbs (800°C, 2 hr, ice brine quenched (IBQ)) in order to maximize ductility. The materials were then lightly pickled and cold rolled to 0.12 in. thickness or cracking, whichever occurred first. After rolling, 1/2 by 1/4 in. specimens were cut for the equilibration anneals given in Table 11 and carried out as previously described.1 Final polishing of the specimens for metallographic examination was done by electrolytic means. Specimens were first examined without etching under bright field and polarized light illumination, for this is the only means of detecting the "two-phase" phenomenon.1,2 The term "two-phase syndrome" refers to Ti-A1 al-loys which appear on the bases of their chemical, phys-ical, and mechanical properties, to be two-phase, but are actually single phase and inhomogeneous in composition. Since processing and heat treatment of the alloys of the first group were completed before the two-phase syndrome was discovered, a number of the specimens were found to exhibit this phenomenon—80 pct of those of the Ti-Al-Zr system, 5 pct of those of the Ti-Al-Sn system, 30 pct of those of the Ti-Al-Zr system. The affected specimens were homogenized by heating above the ß transus temperature and quenching. The heat treatment and working schedules to accomplish this are given in Table 111. After rolling, specimens were pickled (3 pctHF, 30 pct HNO3 in water) to remove 1 to 2 mils from the

Jan 1, 1970

By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work' on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

[Paragraph No. PREFACE ON ASSAYING I BALANCES AND WEIGHTS 2 Balances required for Assaying 13 How assay Weights are made 3 Assay Weights based on the Centner 18]

Jan 1, 1949

[E. E. SCHUMACHER, Chairman ARTHUR PHILLIPS, Past-Chairman L W. KEMPF, Senior Vice-Chairman E. A. ANDERSON, Vice-Chairman H. A. MALONEY, Treasurer FRANK T..SISCO. Secretary 29 West 39th Street, New York 18, N. Y.]

Jan 1, 1946

By David Cornell, Yusuf K. Sukkar

The fundamental differential equation for fluid flow has been rearranged, integrated numerically for natural gases, and the results presented in tabular and graphical form suitable for the direct calculation of vertical gas flow problems. The integration is rigorous except for the use of a constant average temperature. Both static and flowing bottom-hole pressures may be calculated by (his method without resort to trial and error procedures. INTRODUCTION Bottom-hole pressures can be determined either by direct measurement with a bottom-hole pressure gauge or by calculation. Since measurement with a bottom-hole pressure gauge is costly, calculation of bottom-hole pressures is to be preferred when possible. Calculation involves knowledge of the wellhead pressure, the properties of the gas, the depth of the well, the flow rate, the temperature of the gas, and the size of the flow line. These quantities must be combined in a suitable equation for vertical flow. Several equations have been developed for the purpose of calculating gas flow through both horizontal and vertical pipes1,2,4,5,6,7,8,9 These equations all have the basic differential equation for flow as their starting point. They differ only in the assumptions which are made in order to simplify the integration step. The bottom-hole pressures calculated using any of the better known equations are in good agreement with bottom-hole pressures calculated by a more rigorous but considerably more tedious stepwise integration method. All of these methods, however. require a trial and error solution for the calculation of flowing bottom-hole pressures. The purpose of this paper is to present a method which provides a direct solution of static and flowing bottom-hole pressures without use of a trial and error solution. At the same time the method involves fewer simplifying assumptions than any of the previous methods used, except lor the lengthy stepwise method. The derivation of any practical flow equation begins with the basic differential equation which is rigorous for almost all flow problems. The five terms in Equation 1 represent the potential energy, the potential energy of position, the kinetic energy, the shaft work done, and the energy losses due to motion of the fluid respectively. Equation 1 reduces to Bernoulli's theorem for the case of horizontal flow of an incompressible fluid, no work done, and no energy losses due to friction. In the present case, the term (v) (dv)/(g,.) can be shown to be quite negligible compared to the other terms, and is therefore neglected in the derivation. The term — dws includes work done by a pump or turbine in the system and is zero in this case. The frictional losses in the pipe are included in the term — d(lw) which is expressed in terms of the Moody friction factor as in Equation 2. (f) (v2) (dL) d(lW) = (f)(V2) (dl)/(2) (g) (d) The specific volume of a gas can be expressed in terms of the temperature, pressure, molecular weight, and compressibility factor. The velocity of the gas can be expressed in terms of the weight rate of flow, the specific volume, and the dimensions of the pipe.The reduced pressure Pr is to be used because z can be expressed as a function of Pr and Tr alone for most natural gases:

Jan 1, 1956

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By R. W. Armstrong, P. C. Jindal

WE should like to point out that Hu and cline.1 in their study of the recrystallization of titanium, have obtained data which appear very important for accurately determining the dependence of hardness on grain size for this material. It has been proposed2,3 that the macrohardness. H. of a poly crystalline material should depend on its average grain diameter, l. in accordance with the relationship: H =H0 + kHl-1/2 [1] where Ho and kH are experimental constants. This relationship follows from the hardness dependence on yield stress or flow stress4 and. thence. the Hall-Petch stress-grain size relations.5'6 Fig. 1 shows the Diamond Pyramid Hardness. Dph. values vs the reciprocal square root of the average diameter of the recrystallized grains, taken from the titanium data reported by Hu and Cline. The data in this figure give a linear relationship for the hardness over a wider range of grain diameters than anyone has previously measured. The data are not linear, for example. on an I-1 or l-1/3 scale. At the very large grain sizes the data are in reasonable agreement with measurements earlier reported by Holden, Ogden, and Jaffee.7 For the grain sizes smaller than 1 µ, which correspond in Fig. 1 to hardness values greater than 150, the material was reported as not being completely recrystallized and, therefore, these data appear less meaningful as far as the hardness dependence on grain size is concerned. However. it has been suggested by other investigators that deformed materials exhibit strengthening due to an effective grain size refinement even in the unrecrys-tallized condition.8-10 Also. Hu and Cline have shown that a change in texture occurs for titanium during the recrystallization process and. especially. following it. The influence of this texture change on the hardness-grain size relation would be expected to be less than that reflected in the unidirectional stress-strain behavior, even for an hcp material. because of the actual combined stress system which applies for the hardness test. For, at least, certain combined stresses, average values of the orientation factors should still occur in the stress-grain size analysis of a material exhibiting a preferred orientation.' We previously suggested3 that the experimental constants. H0 and kH. from the Meyer hardness-grain size relation should be correlated with the Hall-Petch constants, uoy and ky.5,6 Our recent study" of the Hall-Petch relation and the hardness-grain size results which obtain for a number of polycrystalline materials shows that: The inequality [2] is explained by noting that the hardness should be correlated. perhaps, with the flow stress at some value of strain, as suggested by Dugdale,12 and. also, that the influence of strain on the Hall-Petch relation is to increase uo and not change k very much." Normally. Dph values and Brinell hardness values are nearly equivalent to each other and to the Meyer hardness number. For the case of titanium, then. the inequality [2] may be evaluated using the experimental values of ao = 8.0 kg per sq mm and ky = 1.3 kg per mm3/2 obtained from the experiment of Guard.6,13 Thus, (Ho/uo) = 12 and (kH/k3) = 1.3. This research has been supported at the University of Maryland through the Center of Materials Research by the Advanced Research Projects Agency of the U.S. Government.

Jan 1, 1969

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By Torres S. Ricardo, Encina M. Víctor, Segura O. Claudio

INTRODUCTION This paper is a conceptual resume of engineering studies that have been evaluated by the Mine Department related to production planning over the next twenty-five years. These studies have been required principally because: a) The Rio Blanco Mine, property of CODELCO- CHILE, Andina Division, faces an operational problem due to heavy snowfall in winter which enters the surface subsidence area of the cave; later melts and filters into the broken ore creating a product that is difficult to transfer through the orepasses. The phenomenon is especially serious during the spring and has been increasing over the years. This element that complicates extraction will be controlled with the procedures proposed or others that may be determined in the future. b) The mine will increase production in 1985 by 40% . LOCATION The deposit is located in the central region of the Andes Cordillera, at an altitude of approximately 3,600 m above sea level, 50 km to the northeast of Santiago. The main camp is Saladillo (at 1,300 meters above sea level) located 30 km from the mine. Due to its location, the mine is subject to heavy snow storms during the year. On many occasions the road from Saladillo to the mine is closed because of storms and avalanches. For this reason the company has self-sufficient civil facilities near the mine to cover the needs and welfare of the working force. These housing facilities are connected to the mine by underground passages. For the same weather related reason the primary and secondary crushers, and the entire concentrator complex are located underground. GEOLOGIC CHARACTERISTICS Geology Based on the geologic model developed for the Rio Blanco deposit and comparing it with standard models pertaining to copper porphyries, it can be concluded that this deposit is part of the apical sector of a mega deposit and therefore the projections of the Xio Blanco cop per mine are very favorable, both in lateral area and depth. In order to confirm and evaluate these geo- logic features, an extensive drilling program was started at the Rio Blanco deposit. Diamond drill holes were drilled to depth as well as in the areas named "La Americana", "Don Luis" and "Elguin". The area explored by the drill program is 3 km long in a north-south direction and 1.5 km wide in an east-west direction. In some sections the drilling in depth reached the 2,300 m elevation mark. The lowermost level in the mine is at elevation 3,070 m. These new studies have permitted the recognition of the following lithologic units: Andesite Andesite Breccia Granodiorites, Rio Blanco and Cascada Granodiorite Breccia Quartzmonzonite Porphyry Monzodiorites and Latites Tourmaline Breccia Dacite Pipe and Rhyolite marginal ring. The mineralogical study permits the definition of three stages of hypogene and hydroterma1 alteration of importance with a time-altered sequence. These stages correspond to a late hydrothermal stage. The kinds of alteration that have been recognized are: Potasic Alteration Propylitic Alteration

Jan 1, 1981

By R. G. Paterson

THE usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired size and shape, and in one method' a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averaging a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer's knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. METHOD The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or diamagnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. DESCRIPTION OF APPARATUS Of many alternating-current bridge methods applicable,3 the one shown in Fig. I (Owen's bridge') was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by P1L1. It is connected to the bridge by about

Jan 1, 1941

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.' The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.' In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."' The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory' shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.' Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation' in previous work with high purity aluminum.

Jan 1, 1957

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,'-* iron,' and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

Department of Forestry and Geological Development, 435 State Capitol, Atlanta, Ga. S W. McCalhe, State Geologist. A complete list of Bulletins of the Geological Survey of Georgia will be sent upon request. Forty-five Bulletins have been issued, most of which deal with the mineral deposits of the state and are still available; they may be had on payment of postage. The subject matter of those bulletins of most interest is indicated in the following list, with the year of issue and the mailing weight. Bulletin 1, Marbles (1894), 3 lb , 8, Road building materials (1901), 3 lb , 9, Granites and gneisses (1902), 2 lb ; 10, Iron ores (1900), 2 lb , 11, Bauxite (1904), 2 lb.; 12, Coal deposits (1904), 2 lb ; 13, Ocher deposits (1906), 2 lb.; 14, Manganese deposits (1908), 2 lb ; 17, Fossil iron ore (1908), 2 lb.; 18, Clay deposits

Jan 1, 1933

During the past 60 or 90 days, the metropolitan newspapers have published much concerning unemployment throughout the nation and the efforts of the Army and various other bureaus for finding work for the returning soldiers. The United States Employment Service has 2000 bureaus throughout the country, which Nathan A. Smyth, Assistant Federal Director, states have placed more than 2,400,000 persons in employment. The Engineering Societies Employment Bureau, which, since December, 1918, has been endeavoring to put all returning engineers in touch with employers who need efficient men, has produced results that are very gratifying to the Secretaries of the four Founder Societies under whose direct management the Bureau operates. During this period, 1615 men have registered at the Bureau's office in the Engineering Societies Building; not all of these, however, are unemployed. Many are ex-army and navy men, who in passing through New York on their way home, look over the field in the hope of making a change for their own benefit before returning to their former positions. During this period, 427 positions vacant have been filed, 2300 of which positions have been filled from the men registered. The letters mailed by this Bureau amount to about 1000 a month and the number of personal calls at the office, 1600. The lowest number of positions filled has been in mining, but the lowest number of registrations is also from mining men. While in February idleness throughout the nation was increasing at the rate of 35,000 a week, under date of Mar. 7, Arthur Woods, a special assistant to Secretary of War Baker, states that there is a material improvement in the unemployment situation and that the problem is no longer a serious one. It is recognized that' the improvement wrought in each individual by his military training and experience has so increased his value that it is 'not only unfair, to ask these men to accept their old jobs at the old wages, but it is probably very unlikely that they will be willing to do so. This plain statement of improvement may not carry conviction to everyone but a concrete example will show its validity. Take the example of a young man under 21, bright and intelligent, with only a high-school education who was employed, before being drafted, on purely manual labor. He shows up well under military training and is made a corporal; he makes good and is appointed a sergeant; and finally becomes top sergeant, which requires him in many ways to handle the entire company of 250 men. The result is; even if he has not been tried by the fire of battle, he comes out of the army with a feeling of self-confidence and capacity that was entirely lacking when he went in and he has had actual experience in handling a larger body of men than the average mine foreman at twice his age, and he has had twice the average amount of detail work to take care of.

Jan 4, 1919

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer's knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen's bridge') was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer's knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen's bridge') was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946