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By T. S. Liu, E. A. Peretti

A LITERATURE survey of the In-Sb system, which was made before a study of the binary diagram was undertaken, revealed that the intermediate phase InSb existed and that its crystal structure is face-centered cubic of the zinc blend type. In 1929 Goldschmidt' determined the lattice constant for InSb and obtained a value of 6.452A. A more recent value, 6.461A was reported by Iandelli2 in 1941. The purity of the indium used was not very high, however. The indium used by Iandelli contained 2 pct Ge. In view of this fact it was decided to remeasure the lattice parameter using high-purity indium (99.97+ pct In) and spectrographically standardized antimony of the highest purity available (99.91 pct Sb). Specimens corresponding to the InSb composition were made by carefully weighing the ingredients on an analytical balance and heating them in vacuo in a quartz tube at 700°C. As melting losses were negligible, the alloys were not analyzed chemically, but the intended analysis was taken as being accu- rate. Powder samples were prepared by either filing or crushing of the brittle alloy, followed by screening at 325 mesh. The powders were then annealed at 400°C in evacuated capsules for about an hour. X-ray photograms were taken with a Debye and a back-reflection focusing camera, using characteristic cobalt K. radiation. Lattice parameters were calculated by Cohen's³ method. The results of a Debye pattern and of a back-reflection pattern at 25°C are given in Tables I and 11. The lattice parameter at 25 °C is 6.47602A.

Jan 1, 1952

By Sylvan Z. Beer

Aluminum phosphide was synthesized and grown in solution of excess aluminum using a modified two-temperature technique. An inversion in the density difference between ALP and molten aluminum takes place at about 1100°. Dispersed nuclei can act as sources for further crystal growth in a manner resembling ripening. Advantage was taken of this phenomenon by introducing a stirring motion into the molten liquid. This was done with a split-phase 10-kH2 rotating magnetic field produced by four horizontal coils placed symmetrically about the furnace at the level of the molten metal. The method also prevents the formation of a surface film which would impede the reaction. By this technique vastly improved yields were obtained and flat crystals 5 by 5 by 0.5 mm were grown at lower temperatures and at greater rates than heretofore. THE family of III-V intermetallic compounds has received much attention since the prediction of their semiconducting properties in the early 1950s. Of the family, A1P has perhaps the highest band gap of those compounds normally possessing the zinc-blende structure. But it has been least studied because it is difficult to handle and grow. The handling difficulties have been dealt with elsewhere and it is sufficient to say here that, by various techniques, many of the difficulties can be overcome.' The difficulties encountered in crystal growth can be related to the refractory nature of A1P and in turn to its high band gap. Because of the anticipated high melting point of the material and the accompanying high phosphorus vapor pressure, the reported work on synthesis and growth was done by epitaxial synthesis-growth via chlorine2 and iodine3 transport and from solution of excess aluminum by the two-temperature technique.4'5 The transport-grown crystals take on the dimensions of the substrate but do not grow easily in thickness. In the usual two-temperature technique as applied on the synthesis of Alp, the temperature of the molten aluminum is kept at 1000° to 1250°C while the phosphorus is maintained at 1 to 20 atm. A thin film of aluminum phosphide and oxide form immediately, impeding the reaction and affecting the yield. Attempts to grow the Alp from such solutions by the methods used to grow Gap and InP from excess gallium and indium have not been successful. As discussed in the preceding paper,5 the yield can be greatly increased

Jan 1, 1969

By C. S. Blair

The development of a geological department as an integral part of the Tennessee Coal, Iron & Railroad Co. in the Birmingham district, Alabama, in 1908 was an innovation probably unique for any mining organization south of the Ohio River. At that time a few of the oil companies were starting geological departments, but there were no geologists among the larger industrial organizations. The Tennessee Coal, Iron & Railroad Co. had been a substantial producer of pig iron for many years and was just getting a start in the manufacture of steel products from the pig iron. It had large acreages of coal land, ore land and timber land, but there was lacking the detailed knowledge of the possible mineral resources of much of its territory, and this territory at that time covered an area in the neighborhood of 500,000 acres in the states of Alabama, Tennessee and Georgia. Those responsible for the operations of the mining properties, not being familiar with the kind of help that might be expected from geologic work, were decidedly skeptical of the utility of the work. Therefore it was necessary to develop cooperation with the mining organization, by not infringing upon its functions, and by developing the work in such a manner as to demonstrate to the mining department its practical utility. In the first instance the man responsible for a mining operation is apt to assume the attitude that the geologist is a blockader, because the geologist, unfortunately, is obliged to point out difficulties in the carrying out of mining operations in the way originally planned. He points out the dangers of mining out one coal or metal seam at the ultimate expense of an upper or lower seam, and he develops structural features, such as faults and folds, which call to the attention of the mining operator difficulties in his future operations, which the latter had not anticipated. Eventually, however, the value of having these data became apparent to the Tennessee Coal, Iron and Railroad Co., and the operators not only welcomed the geological work and cooperated fully in its acquisition of essential information, but reached the point of asking assistance and advice; and complete coordination of the two activities has existed for many years.

Jan 1, 1935

By C. S. Blair

The development of a geological department as an integral part of the Tennessee Coal, Iron & Railroad Co. in the Birmingham district, Alabama, in 1908 was an innovation probably unique for any mining organization south of the Ohio River. At that time a few of the oil companies were starting geological departments, but there were no geologists among the larger industrial organizations. The Tennessee Coal, Iron & Railroad Co. had been a substantial producer of pig iron for many years and was just getting a start in the manufacture of steel products from the pig iron. It had large acreages of coal land, ore land and timber land, but there was lacking the detailed knowledge of the possible mineral resources of much of its territory, and this territory at that time covered an area in the neighborhood of 500,000 acres in the states of Alabama, Tennessee and Georgia. Those responsible for the operations of the mining properties, not being familiar with the kind of help that might be expected from geologic work, were decidedly skeptical of the utility of the work. Therefore it was necessary to develop cooperation with the mining organization, by not infringing upon its functions, and by developing the work in such a manner as to demonstrate to the mining department its practical utility. In the first instance the man responsible for a mining operation is apt to assume the attitude that the geologist is a blockader, because the geologist, unfortunately, is obliged to point out difficulties in the carrying out of mining operations in the way originally planned. He points out the dangers of mining out one coal or metal seam at the ultimate expense of an upper or lower seam, and he develops structural features, such as faults and folds, which call to the attention of the mining operator difficulties in his future operations, which the latter had not anticipated. Eventually, however, the value of having these data became apparent to the Tennessee Coal, Iron and Railroad Co., and the operators not only welcomed the geological work and cooperated fully in its acquisition of essential information, but reached the point of asking assistance and advice; and complete coordination of the two activities has existed for many years.

Jan 1, 1935

By V. Koump, T. F. Perzak, R. G. Olsson

The vate of dissolutioz of carbon in molten Fe-C alloys urns studied by votating- cylindrical g-vaphite sairlples in a stationary crucible containing the melt. The rate of dissolltion was determdined from the change in the bnth co)npositiorz. Alccss-tvansfev coeffi'cients, calcilated with the assurlption that the inte)yacial liquid ulas saturated with carbon, were found to be in agreement with an existing Correlation fov mass transfer jroni votating cylinders. It is corzcllrded tlat, itz the wnge of- Reynolds' numbers itzvestigated (790 to 18,000), the vate of dissolutio of carborz in Fe-C alloys is controlled by tile rate of carbon difirsion from the interface. The dissolution of carbon in molten Fe-C alloys has been the subject of a number of investigations. Most of these investigations have been inconclusive because of poorly defined experimental variables. Two of the more sophisticated studies are summarized below. Dahlke and Knacke' studied the phenomenon by, in part, immersing graphite rods into 0.5 pct carbon-steel for different lengths of time. Since the experiments were conducted in air or in CO atmospheres, the melt was strongly agitated by gas evolution. It was concluded that the change in bath composition as a function of immersion time was in agreement with the assumption that the dissolution process was transport-controlled. The hydrodynamic conditions in these experiments, however, were not well-defined and gave no indication of the nature of the dissolution process at higher fluid velocities. In a recent study Shurygin and ruk investigated the dissolution of carbon in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Small graphite disks were rotated in a crucible containing molten alloys under such conditions that only the lower face of the disk was exposed to the melt. The results of this investigation indicate that, over the range of velocities (100 to 1000 rpm) and bulk liquid concentrations (0.7 to 4.5 wt pct C) considered, the dissolution of carbon in the iron alloys is limited by the diffusion of carbon from the interface to the bulk liquid (a transport mechanism). For the particular geometry used by these authors, exact analytical solutions of hydrodynamic and diffusion problems are aailable. Hence the experimental results obtained by Shurygin and Kryuk permit the evaluation of diffusion coefficients of carbon in the four systems investigated. In the present investigation a series of experiments were conducted in which the rate of dissolution of carbon in Fe-C alloys was measured under conditions which permitted wide variation of the fluid velocity and the carbon concentration of the bulk liquid. Graphite cylinders were rotated at different speeds in a stationary concentric crucible containing various molten Fe-C alloys. THEORETICAL DEVELOPMENT In general, the resistance to mass transfer from a solid interface to a turbulent liquid is assumed to reside in a laminar boundary layer adjacent to the interface. If it is also assumed that the diffusion coefficient is independent of concentration, the steady-state rate of dissolution for the case of arbitrary liquid and solid densities can be obtained from the integration of the equations of continuity. The derivation is similar to that used by Lommel and chalmers4 for the case of pl = ps. The solution, expressed in terms where N = rate of diffusion of the solute from the interface. Exact analytical solutions of the hydrodynamic equation for the boundary layer thickness are available for only a limited number of geometries. Consequently, a mass-transfer coefficient, k, is usually

Jan 1, 1967

By Sylvain Pirson

THE number of seismograph field crews employed in the active survey of potential oil territories is still on the increase, owing to the ever pending threat of a shortage in the supply of crude oil. It is to be expected that for years to come the seismograph will be responsible for discovering many new oil fields, both in wildcat territories and in deeper formations, and that the seismographic campaign will go on unabated. Yet improvements in instrumental design, in the field and interpreta-tive techniques, are brought about year after year, and lead to the reshooting of areas many times surveyed previously. Notwithstanding the experience gained by the past eight years of active work in reflection seismographic surveys, the results given by this method of mapping deep formations have in many instances been at variance with the information subsequently obtained by the drill. To overcome this shortcoming, geophysicists have used closer spacing of the shot points and closer control of the depth points. The method dis-cussed here is being used actively in the Mid-Continent region and endeav-ors to reduce the interpretation work to a mere mechanical technique, leaving as little as possible to the opinion of the interpreter.

Jan 1, 1937

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald' who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall' who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956

By Edgar G. Tuttle

The accompanying figures show the arrangement of a twocompartment excentric jig fitted with adjustable and automatic discharges for drawing oft' the lower product obtained in jigging minerals, ores, coal, etc., which is designed to remove or separate more effectively the materials treated, as they travel over the jig from the receiving- to the discharge-points.

Jan 1, 1897

MINING ENGINEERING presents the annual membership report of the Society of Mining Engineers; see page 147.

Jan 7, 1964

By W. A. Wood, H. L. Wain, R. I. Garrod

The mechanical behavior of recrystallized chromil~m of high purity has been studied, principally in torsion and to a lesser extent in tension, at temperatures between —196oand 350oC. Depending upon the conditions of test, the material may show brittle or ductile behavior or an intermediate or subduc-tile state having some of the characteristics of each. This latter state existed at temperatures between approximately ±50°C and was characterized by a) extensive creep at stresses well below the normal fracture stress, b) nonelastic loading/unloading effects during creep, c) strain softening under cyclic loading, and d) final failure of a brittle type. Suggestions are made on the dislocation processes and interactions which give rise to subductile behavior The ductile-brittle transition in bee metals has been studied mainly by tension and bend tests. These methods, however, favor crack propagation which may follow too closely on initiation for detailed study of the transition itself. For work of this nature, therefore, other modes of deformation less favorable to crack propagation may be preferable. This paper describes a study of the ductile-brittle transition in chromium which is based mainly on torsional testing although a few subsidiary experiments were made in tension. It appears to reveal at the transition an intermediate state that cannot properly be described as either brittle or ductile. Torsional tests on chromium have been made by other workers1 but not, as here, primarily for study of this intermediate state. EXPERIMENTAL The chromium, in the form of swaged rod, was prepared by techniques already described.' The particular material used was one in which the main impurities were 0.03 wt pet 0 and 0.006 wt pet N and one in which transition from ductile to brittle states in torsion conveniently fell at about room temperature. For torsion, test specimens were from 5/16-in.-diam rod to provide test portions 1-1/4 in. long by 7/32 in. diam, a twist of 1 deg thereby corresponding throughout this paper to 0.0015 surface shear. The specimens before test were annealed for 2 hr at 1200°C in vacuo, which left them with a re-crystallized grain size of about 0.01 mm, and then electropolished. They were tested under dead-weight loading in an apparatus in which they could be surrounded by a furnace or cooling chamber, tests in practice being made at various temperatures between -196" and +350°C. For tension tests, cylindrical specimens were prepared in a similar manner and tested at room temperature under dead-weight loading. RESULTS (TORSION) Subductile State. The state described above as intermediate between brittle and ductile may be perhaps best defined by reference to torque/twist curves at various temperatures. These are grouped in Fig. 1. Below about -50°C the material was brittle, in the sense that it exhibited little plastic deformation under stress and fractured by cleavage along planes of maximum resolved tension, which in torsion produces the well-known helical type of fracture. The deformation is typified by the curves for -196" and -150°C in Fig. 1; it shows a slight but progressive deviation from linearity above a certain torque, here about 50 lb-in., until fracture occurs at about 95 lb-in. A feature to which it is desired specially to call attention is that under none of the loads did the specimens show significant creep.

Jan 1, 1964

By Leonard Greenburg

The American literature in the field of dust sampling and analysis has been growing rapidly since 1915. Studies made since that time clearly indicate that there are three fundamental factors that determine the production of lung pathology due to dust inhalation. These are the duration of exposure, the chemical and mineralogic nature of the dust and the concentration of the potentially harmful dust. In the estimation of the amount of the potentially hazardous dust there are essentially three problems involved: (I) a determination of the size of the hazardous dust; (2) determination of the most satisfactory apparatus and technique of sampling, and (3) the most satisfactory method of analysis. A complete study of the literature shows that industrial dust varies ill size from ultramicroscopic particles to those larger than lop in diameter and that relatively few particles are found over 5u in diameter. Approximately 10 to 25 per cent are less than 0.811 in diameter and the median size as a rule is found to lie between 1.25 and 1.75 microns. From the point of view of lung pathology the particle sizes of most importance lie between 0.5 and 5u. Of all the instruments for sampling dust the Impinger apparatus is the only one that will sample a larger body of air satisfactorily with small control errors and high efficiency in both low and high concentrations of dust. The Owens apparatus has the advantage of being more portable and somewhat easier to use but it does riot permit of the sampling of large volumes of air. It has a low efficiency in high concentrations of dust and does not permit dust weights to be obtained. From the point of dust-counting technique the author points out that in 1922 considerable experimentation with dark field and oblique illumination resulted in the conclusion that such methods were not readily duplicated from day to day and therefore yielded somewhat erratic results. Changes in the amount of illumination produced variations of several hundred per cent in dust counts obtained with dark ground

Jan 1, 1934

By W. Rostoker

IN the course of the development of the phase equilibrium diagram for the system Zr-Cr,' the structure of an as-cast allov having the composition ZrCr2 was analyzed and established to be isomorphous with MgZn2 (C14, hexagonal lattice, 12 atoms per unit cell). In a recent paper on the same system, Hayes, Roberson, and Davies' report for the ZrCr2 phase an isomorphy with MgCu2 (C15, cubic lattice, 24 atoms per unit cell). It appeared that this conflict might be resolved by assuming a high and low temperature modification for ZrCr2. That this was the case with the phase TiCr2 has recently been demonstrated by Levinger." Specimens of ZrCr2 annealed at 1200°, 1100°, 994", 900°, 834", 800°, and 700°C, respectively, and subsequently quenched were examined by X-ray diffraction analysis. It was successfully demonstrated that a transition from the MgZn, structure at lower temperatures to the MgCu, structure did occur at some temperature between 900" and 994°C. Table I lists the observed structures at the various annealing temperatures. In Table II, a summary of line spacings and intensities is given for each of the allotropic modifications. The first six lines of the MgCu2 structures have been located in the table to illustrate the close similarity between the patterns. Lattice parameters of the two modifications were calculated by a least squares solution of equations for interplanar spacings for a series of high angle lines. The results are as follows: MgZn2 type - c = 8.262 kX, A = 5.079 kX. MgCu2 type — a = 7.195 kX. It is interesting to note that TiCr2 behaves in reverse fashion yn that the MgCu, structure is the low temperature modification and the MgZn2 structure is the high temperature modification. References lR. F. Domagala, D. J. McPherson, and M. Hansen: This issue p. 279. 'E. T. Hayes, A. H. Roberson, M. H. Davies: Trans. AIME (1952) 194, p. 304; Journal of Metals (March 1952). 3B. W. Levinger: Trans. AIME (1953) 197, pp. 195-196; Journal of Metals (February 1953).

Jan 1, 1954

Mining Methods GERALD F. SHERMAN, Chairman CHARLES F. JACKSON, Vice-chairman Alluvial Mining CLINTON BERNARD H. R. NORSWORTHY - O. B. PERRY Open-cut Mining Iron MAX H. BARBER J. A. MACKILLICAN Copper MICHAEL CURLEY R. B. TEMPEST Underground Mining Iron C. H. BAXTER TENNEY C. DESOLLAR Copper W. B. DALY R. W. THOMAS

Jan 1, 1936

By A. E. Dwight, A. F. Berndt

Binary and ternary alloys of uranium with transition metals were prepared with U2X stoichiometry. The compounds U2Tc, U2Rh, U2Os, and U2lr were formed by peritectic or peritectoid transformations, and were shown to be isostructural with U2Ru. The lattice constants are presented. Miscibility relationships obtained from the study of ternary alloys are graphically summarized in terms of an area-of-stability plot. The compound U2Re is not isostructural with either U2Ru or U2Mo. A series of compounds with stoichiometry U2X has been prepared in which X is technetium, rhodium, rhenium, osmium, or iridium. The only other U2X compounds, for which X is related to the above transition metals by proximity in the periodic table, are U2Mo and U2Ru. The structure of U2Mo is the tetragonal C11b type (MoSi2 type)1 and U2Ru is monoclinic, with a new structure type.' This investigation was undertaken to determine if any of the above compounds are isostructural with either U2Ru or U2Mo and to find the range of occurrence of these phases. EXPERIMENTAL Alloys were prepared from stoichiometric amounts of electrolytic uranium (99.99 pet pure) and transition metals of 99.5 pet purity (98+ pet pure Tc), by arc melting on a water-cooled copper hearth under an Ar-He atmosphere. Weight losses were negligible. The buttons were homogenized at temperatures between 700o and 800°C (900°C for U2Tc) in evacuated capsules and air-cooled. The X-ray powder specimens were annealed briefly at the temperature of homogenization. Except in the case of the technetium alloy, metallographic examination was used to determine the number of phases present. The radiation hazard involved in handling technetium precluded the use of metallography to examine U2Tc. The temperature and mode of formation of the U2X phases were determined by heating the metallographic specimens to successively higher temperatures, until examination indicated the presence of chilled liquid or a peritectoid transformation. RESULTS The U2X compounds investigated were found to be formed under the following conditions: UzTc unknown U2Ru peritectic 897o ± 3°C U2Rh peritectoid 755o ± 5°C U2Re peritectoid3 below 750°C Uas peritectic4 920°C U2Ir peritectoid 775o ± 5oC Debye-Scherrer patterns for the above U2X phases were made with CuKa radiation (nickel filter). The similarities in the positions and intensities of the strongest lines in the front-reflection region strongly suggested that U2Tc, U2Ru, U2Rh, U2Os, and U21r are isostructural with only minor differences in the unit-cell dimensions. The known lattice constants and intensities of the Debye-Scherrer rings for U2RU2 were used as a guide in order to index the low-angle X-ray reflections of the U2TC, U2Rh, U2Os, and U2Ir powder patterns. Approximate lattice constants for these compounds were thus obtained and were used along with the intensities observed for U2Ru to index the strongest lines in the back-reflection regions. A sin2 2? correction term was included and the lattice constants were refined and standard deviations estimated by least squares. Comparison of observed and calculated values of Q(= 4 sin2?/?2) used in these calculations are given in Table I. In each case when the positions of lines could not be resolved on the films they were not measured. The final lattice constants, with their standard deviations, are given in Table 11, along with the unit-cell volume and X-ray density. The values of the atomic volume5 of the transition ele-

Jan 1, 1965

United Engineering Society ARTHUR S DWIGHT J VIPOND DAVIES J V N Dorm Engineering Societies Library Board SIDNEY H BALL ALEXANDER C HUMPHRFYS GEORGE C STONE JOHN H JANEWAY Engineering Foundation Board H M BOYLSTON J VIPOND DAVIES GALEN H CLEVENGER Society for Promotion of Engineering Education WILLIAM KELLY ALLEN H ROGERS

Jan 1, 1923

[United Engineering Society ARTHUR S. DWIGHT J, VIPOND DAVIES J, V, N. DORR Engineering Societies Library Board SYDNEY H. BALL ALEXANDER C, HUMPHREYS GEORGE C, STONE JOHN H, JANEWAY Engineering Foundation Board H. M. BOYLSTON J. VIPOND DAVIES GALEN H, CLEVENGER Society for Promotion of Engineering Education WILLIAM KELLY ALLEN H. ROGERS]

Jan 1, 1928

By A. Styka, G. Fischer, S. Tour

Described herein are the results obtained during research work involving coating titanium alloys with molybdenum by vapor-deposition methods. Results show that the method can be used successfully to deposit hard adherent wear-resistant coating of methodmetallic molybdenum on titanium or titanium alloys without changing the microstructure of the titanium base. PRODUCTION and use of titanium and its alloys have increased tremendously in the past few years. The physical, mechanical, and chemical properties of this engineering metal have caused considerable enthusiasm among metallurgists and engineers. However, as with all materials, there are some drawbacks. For example, titanium is susceptible to seizing and galling on wearing surfaces. In order to produce a good wear-resistant surface, many investigations have been conducted evaluating oxidizing, carburizing, nitriding, carbonitriding, sili-conizing, and chromizing of titanium. All of these processes require high temperatures for rather extensive periods of time. It has been possible to produce hard surfaces on titanium and its alloys by a number of these processes at the expense of a deterioration of the physical properties of the base material. A practical solution to the problem of providing titanium and titanium alloy parts with a satisfactory wear-resistant nongalling surface must be one that does not involve excessive temperatures for long periods of time. Sam Tour & Co. Inc. has completed a research and development contract for the United States Army Ordnance Corps on vapor deposition of molybdenum on titanium and titanium alloys. On the basis of results obtained from the research program, titanium alloys can be coated successfully with molybdenum to provide a hard wear-resistant surface without harm to their base mechanical properties. The remainder of this article is a description of the techniques used to apply the coating and the results obtained from wear tests on molybdenum-coated titanium. Theory Basically, the technique used was the application of molybdenum by a vapor-deposition method, thermal decomposition of molybdenum hexacarbonyl [Mo(CO)] with hydrogen as the carrier gas. The selection of this method was based chiefly on the following considerations: 1—low plating temperature which would minimize excessive grain growth, 2— low decomposition temperature of the carbonyl, 3— possibilities of controlling the hardness of the plate by adjusting the carbon content using the plating temperature and pressure as the primary variables, 4—use of high vacuum, thereby avoiding unnecessary oxidation and other complex reactions with the atmosphere. Free energy data1 show the strong tendency for titanium to combine with O2 N2 or carbon from normal temperatures to temperatures above its melting point. To maintain the titanium in a film free condition, the use of as high a vacuum as possible is indicated. The literature' indicates that the reaction product of hydrogen with titanium is unstable in vacuum at around 400°C. 5—Although it is indicated from the thermodynamic standpoint that there is little possibility of removing carbon from either titanium or molybdenum, the work of Lander and Germer -ndicates that the use of a suitable H,/CO ratio is somewhat effective in minimizing carbon deposition. 6—Availability of molybdenum carbonyl. In the simplest form, the conditions of equilibrium3 in chemical reactions involving decomposition of carbonyl are as follows: Mo (CO) ? Mo + 6CO 2CO * C + CO,. The plating rate is proportional to the rate of evolution of CO from the decomposed carbonyl, i.e., it is proportional to the pressure of the gaseous decomposition products. Carbon released from CO gas is the significant constituent for the variability of the physical properties of the product. High carbon deposition is favored by increasing pressure. Limitations are imposed in the selection of plating temperature and pressure. Excessive temperature re-

Jan 1, 1956

PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY. EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 5, 1918

EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS W M Peirce, Chairman Philip Kraft, Vice-Chairman Francis B Foley Hjalmar W Johnson Thomas G Moore ENDOWMENT Cleveland E Dodge, Chairman C F Kelley John D Bradley Harvey S Mudd J Coulter W A Sinsheimer N Eavenson Wilfred Sykes C Jackling Clyde E Weed

Jan 1, 1951

By Franz Posepny

CONTENTS. Introduction. Part I. General Facts And Theories. [ ]

Jan 1, 1902