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By D. V. Doane, G. A. Timmons, W. G. Scholz

Molybdenum of high purity can be produced by direct dissociatiott of commercial molyhdenm disulfide in vacuo at 1600° to 1700°C (2910° to 3090°F). The Product is lower in oxygen than commercially available molybdenzdm powder. Analyses of ingots arc-cast from commercial molybdenum powder, hydrogen-re-cluced from animonium molybdate, and from thermally dissociated molybdenum disulfide indicate that the levels of chemical impurities in these ingots are similar. Equipment now in operation will produce 100-lb hatches of powder product. The paper describes development of processing equipment, control of processing varzahles, handling of the product, and evaluatiotl of the melal produced. MOLYBDENITE (molybdenum disulfide) can be decomposed by heat in the absence of oxygen to produce elemental molybdenum and sulfur, which is evolved as a gas. The temperatures required for the dissociation are above 1370°C (2500°F); the sulfur must be continuously withdrawn to permit the reaction to proceed to completion. This is accomplished by continuous evacuation of the thermal dissociation chamber and condensation of the gaseous sulfur in another part of the system. Cognizance of the fact that the dissociation takes place in two steps is important in controlling the process. Basically, the molybdenite dissociation process has two potential advantages as a method of produc- ing pure molybdenum: 1) The materials entering into the process contain little or no oxygen. Since the process is carried out in vacuum at high temperature, the quantities of interstitial oxygen, nitrogen, and hydrogen in the product should be very low. 2) The process is more direct than the commercia1 method of producing high-purity molybdenum. In the conventional process, molybdenite is roasted to molybdic oxide, the oxide is purified first by sublimation, then by conversion to ammonium molybdate, and finally, the molybdate is reduced in a hydrogen atmosphere (usually in two steps) to the metal lic molybdenum powder. This paper presents a description of the stages in scaling-up of the dissociation equipment and an account of attempts to evaluate the molybdenum produced by thermal dissociation, rather than a report of a fundamental study of the dissociation reaction. Since little has been written on the subject, it is appropriate, before detailing the development of the process, to review briefly the research that has been conducted over quite a period of years. LITERATURE SURVEY The first accounts of the possibility of thermal dissociation of the mineral molybdenite were re-

Jan 1, 1962

By Y. A. Topkaya

The placer gold occurrences at Sart Çayl, Manisa, Turkey, the legendary River Pactolus of King Croessus, were evaluated in this study to determine if this deposit contains sufficient recoverable value to justify development and exploitation. The gold occurs both in the upper Neogene conglomerates and the alluvium derived from these conglomerates. The total reserve in the whole region is estimated to be 500 million cubic metres. Samples were taken of the upper conglomerate and in the alluvium in an attempt to determine the amount and the physical nature of the gold. The gold in samples was recovered by screening out barren oversize followed by washing the sand and gravel through riffled sluices. The resulting sluice concentrate was later panned and amalgamated at site. Laboratory cyanidation testing of some samples for control purposes was also done. The average calculated free gold was found to be about 90-100mg/m3 and the size of gold flakes found was quite small. The field as well as laboratory testing of the samples of Sart Çay1 indicated that the potential reserves in this region could only be developed as a sand and gravel operation and the gold could be recovered together with the heavy minerals as a byproduct.

Jan 1, 1984

By Carl F. Floe, Michael B. Bever

THE possibility that carbon may be soluble in copper to a limited extent has been recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are frequently used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. REVIEW OF LITERATURE In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of o.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.92 58 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been in prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as o.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1945

By A. T. Aldred, K. M. Myles

The vapor pressure of chromium over solid V-Cr alloys has been measured by the torsion-effusion method in the temperature range 1450" to 1650°K. The chemical activities as well as the free energies, entropies, and enthalpies of formation of the alloys have hem computed from the vapor-pressure data. The activities of both chromium and vanadium exhibit fairly small negative deviations from Raoult's law over the entire composition range. The values of the excess entropies and the enthalpies of formation found at 1550°K are considered in terms of the changes in the clzaracteristic properties of vanadium and chromium that occur upon alloying. RECENT interest in the theory and properties of transition-metal alloys has shown the need for relevant thermodynamic data. The present investigation of the V-Cr system was undertaken as part of a more general study of thermodynamic properties of transition-metal alloys. The system was chosen because of the reported complete solid solubility of the components at all temperatures1 and because the difference in magnitude of the vapor pressures of vanadium and chromium allowed a simple effusion technique to be used. The torsion-effusion method was employed to minimize compositional changes in the alloys during the experiments. EXPERIMENTAL Equipment. The torsion-effusion apparatus, shown diagrammatic ally in Fig. 1, consists of a torsion system suspended inside a vertical vacuum chamber whose lower end is surrounded by a high-temperature vacuum furnace. An auxiliary optical lever and screen are used to determine the angle of rotation of the effusion cell. The torsion fiber is an annealed, high-purity, tungsten wire usually between 0.003 and 0.007 cm in diameter and about 43 cm long. The wire supports a concave mirror and a rigid tantalum connector tube. The effusion cell is fastened to the lower end of the connector tube by a dovetailed yoke and har- ness arrangement. The cells, which are 1.27 cm in diameter and 4.4 cm long, were made by electron-beam welding tantalum endcaps onto a 0.025-cm-wall tantalum tube. The two orifices, formed by drilling, have similar areas ranging from 0.011 to 0.031 sq cm. The noninductive sheath-type furnace consists of a single-phase tantalum heating element 6.35 cm in diameter, 15 cm high, and 0.013 cm thick; the element is completely surrounded by radiation shields in an evacuated chamber. The power system includes a 17-kva self-saturating saturable core reactor with an integral magnetic amplifier and a water-cooled, 15-kva, step-down power transformer with a multitap secondary. Temperatures are controlled to within ±1/2o at 1600°K by means of a unit that includes a reference voltage source, a dc electronic null detector, a current-adjusting proportional band relay, and the self - saturating reactor. At 1650°K the temperature variation within the cell, vertically and horizontally, is 3/4oK. Unwanted motions of the torsion system are damped by the movement of an aluminum vane, which is mounted on the connector tube, between the poles of an electromagnet. When not in use the magnet is withdrawn and rotated 90 deg to prevent its interaction with the rotation of the system. Measurements. The vapor pressure, p, is re-

Jan 1, 1964

Mining and oil industry representatives are scheduled to testify May 15 at hearings on the Simpson bill to extend the Reciprocal Trade Agreements Act, Several Congressmen have introduced bills to extend present trade agreements without modification. Price of copper appears to be stabilizing at 30[] per lb, after a period where market price ranged from 27 to 34[]. Copper offerings from abroad were finding no takers at 30.24[] per lb late in April.

Jan 5, 1953

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Pradeep K. Rohatgi, Clyde M. Adams

Dendritic aggregate of ice formed on freezing of aqueous soluitions has been studied. Chlorides of sodium, potassiutn, lithiunz , and hydroget1 were used as solutes. The spacing between ice platelets or den-drites was experimenlally found proportzonal to the square root of freezing time when the freezing rate was constant from beginrting to end of solidification; the constant freezing rates were obtained during freezing of small droplets of aqueous soliitions surrounded by relatively large heat sinks. The transverse growth velocity of the ice platelets is proportional to the square root of the freezing rate. During unidirectional freezing from a constant temperuture chill, the solution at each location is subjected to a spectrum of freezirtg rates. The freezing rate is ini- FREEZING of solutions has been a subject of investigation in many disciplines. Aqueous solutions offer the advantage of transparenty; their study is of special significance due to the increasing interest in freezing processes for desalination. In addition dendritic solidification of aqueous solutions is in many ways analogous to freezing of metallic solutions. Aqueous solutions of most ionic salts freeze with tially low, passes through a maximum, and then decreases until solidificatimz is complete. The den-drite spacing increases linearly with the distance from the chill surface; it is inversely profiortional to the square root of the maximum freezing rate. The dendrite spacings in the two systems (the constanl freezing rate and the varying freezing rate) are equal, when the maximum freezing rate of the varying freezing rate system equals the average freezing vale of the constant freezing rate system. Mass transport in interdendritic liquid duriug solidificatiotz is analyzed; the experimental observations indicate that maximum concentration difference (AC) and supercooling (AT) in the interdendritic liquid are indepexdent of freezing rate. the separation of practically pure ice crystals from the liquid phase; with very few exceptions there is no solid solubility of ionic salts in ice. As an ice crystal grows there is rejection of solute from the moving interface into the liquid. Since the rejected solute moves primarily by diffusion, concentration gradients are established in the liquid. The highest solute concentrations are found in liquid immediately adjacent to liquid-solid interfaces and lowest concentrations farthest from the interface. Two-phase equilibrium obtains only at the solid-liquid interface; at other locations the liquid becomes supercooled because temperature gradients are negligible compared to concentration gradients. This is an immediate consequence of the fact that thermal diffusivities are considerably higher than mass diffusivities.

Jan 1, 1968

By L. F. Mondolfo

An aluminum-copper 4 pct Cu alloy aged at room temperature for times increasing up to 78,000 hr was annealed at 170°C and the hardness and electrolytic potential determined during retrogression and subsequent aging. It was found that there is a change of behavior with increasing time of aging at room temperature which indicates that, given sufficient time, retrogression disappears and the room-temperature aging tends to progress directly into the high-temperature aging. WHEN an age-hardenable alloy is aged at low temperature after proper quench, changes of properties and structure take place. If this material is then heated to a temperature higher than the previous one, but still well below the solution-treatment temperature, the properties and structure changes produced by the low-temperature aging disappear and the material apparently reverts to the as-quenched condition, ready to undergo aging from the start. This phenomenon is termed reversion or retrogression. First discovered by Cayler3l it has been extensively investigated, as shown by the number of publications listed in the bibliography. From all the information available the following facts emerge: 1) All aeg hardenable alloys can be retrogressed.9 13, 19) 24, 33, 41, 42, 44, 47, 53, 54, 61, 63, 64, 66, 73, 78 2) All the properties changes that take place during aging at low temperature can be retrogressed to a smaller or larger extent.4,5,7,12,19,32,49,50,57,58,60,67,75,76 67, 75, 76 3) Retrogression requires that the temperature be well above the preliminary aging temperature. If the difference between the two temperatures is small, Little or no retrogression takes place.7,20,32,33,41,49 57. 65 4) The larger the difference between the preliminary aging and the retrogression temperature, the faster and more complete is the retrogression.20, 33, 41, 48, 65, 67 5) Retrogression can be produced several times in the same alloy.23, 35,41,57,59 6) The amount of retrogression that can be obtained depends on the aging temperature. Alloys aged at the lower temperatures can be retrogressed the most. The higher the preliminary aging temperature the less retrogression can be produced.20,25,33,37,44,49,54,58 7) Appreciable retrogression after aging at elevated temperatures is possible only if the preliminary aging has lasted a short time. After a certain time of aging at high temerature retrogression does not take place any more,:5,6,9,10,11,21,40,58 8) During retrogression the Guinier-Preston zones redissolve and disappear. The other precipitate

Jan 1, 1960

By P. J. Soltis

Direct as well as indirect evidence of a-phase ordering was found in a "near-a" type titanium alloy, Ti-8Al-1Mo-1V. The annealed alloy showed an anomalous decrease in second-stage creep rate at 950°F (510°C) and 47,500 psi. Anomalous increases were noted in initial yield stress after 500 hr creep exposure and in tensile strength after 1100 hr creep exposure. Debye-Scherrer X-ray diffraction patterns obtained on fine-grained polycrystalline speci-ment showed much line broadening and development of superlattice lines after 500 hr at 510° C. Examination with the light and electron microscopes failed to reveal phase changes in thermally exposed material, but detailed metallography is presented illustrating the plastic and fracture characteristics of the alloy. Electron-metallographic evidence is presented, however, which shows the nature of the nucleation and growth of ordered regions from the disordered a in annealed material. In the original phase diagram of the binary Ti-Al system constructed by Ogden et al.1 aluminum was shown to be soluble in a titanium over a wide temperature range at concentrations up to about 30 pct. Subsequently, a number of papers2-7 have appeared which indicate the existence of either intermetallic compounds and/or ordered phases in the a field up to 25 pct Al. In the most recent of these, Goldak and Gordon paw7 have determined unequivocally the ordered hexagonal D019 structure for Ti3Al in a 25 pct Al alloy. No superlattice lines were observed above 1112°F (600°C). Previously, the embrittle-ment encountered by Crossley and Carew4 in low- temperature heat treatments of binary Ti-Al alloys low in aluminum had been attributed to the appearance of a new phase in light micrographs. In the present work, direct as well as indirect evidence is presented showing the existence of a-phase ordering in what is essentially the binary Ti-8A1 alloy containing small percentages of the ß stabilizers molybdenum and vanadium, i.e., the "near-a" Ti-8Al-1Mo-1V alloy. Although Bohanek and Kessler8 have shown that this alloy has good stability at temperatures up to 1100°F (593°C), the present work shows instability at 950°F (510°C) where long exposure times were used. Light and electron microscopy proved very useful in revealing the mechanical behavior of ordered a and led to the conviction that ordered "near-a" alloys may have remarkably good properties and useful engineering applications.

Jan 1, 1965

By J. H. Hamilton, J. R. Lewis, J. H. Dismant, W. M. Fassell

RECENTLY this laboratory undertook the task of preparing some low carbon metallic cobalt by the carbon reduction of precipitated cobalt oxides. The oxides came in two lots and had the compositions given in Table I. Industrially, cobalt rondels' are made by the carbon reduction of cobalt oxide in small reverberatory furnaces at temperatures near but not above 1050 °C. This is a slow and tedious small batch process but does give cobalt metal which is low in carbon (1 pct C). Inasmuch as these cobalt oxides were relatively low in copper and iron it was decided to reduce them with petroleum carbon in a small three-phase electric arc furnace of about 3 to 5 Ib of metal capacity. It was hoped such a procedure would save considerable time and perhaps also indicate an improved commercially feasible process. The furnace was preheated by using small pieces of carbon electrodes to maintain the arc until a temperature of 1500°C was reached. The broken pieces of electrodes were then removed and 500 g of the cobalt oxides and 60 to 100 g of petroleum coke added. At the end of the reduction reaction, a high lime flux was added to the furnace to facilitate the removal of sulphur. Due to the fineness of the cobalt oxide powder used and also to the presence of chlorides there was considerable dust lost in charging the furnace. This was overcome by preparing briquettes composed of the cobalt oxides, charcoal, and a little bentonite to serve as a binder. The results obtained are summarized in Table 11, which shows that the cobalt metal produced in the arc furnace was high in carbon varying from 2.5 to 3.5 pct. This, of course, is much too high. For certain uses, such as in the preparation of permanent magnets, the carbon content of cobalt must be low. It was necessary therefore to find an effective method of reducing the carbon content of the cobalt that had been prepared in the arc furnace. Van Arkel3 recommends the use of Co2O3 as a means of removing carbon from cobalt. Experiments by the authors indicate that carbon is removed with difficulty by this method. Other methods used, including lancing of the molten high carbon cobalt with a jet of oxygen, proved to be ineffective. The method finally used makes use of the fact that cobalt metal is decarburized by carbon dioxide at the temperature of the molten metal. Two methods were used: 1—carbon dioxide was bubbled up through the molten cobalt, and 2— molten cobalt was maintained in a carbon dioxide atmosphere. In the first method the gas was introduced below the surface of the molten metal by means of a quartz tube. A high frequency induction furnace was used to keep the cobalt molten in both of these experiments. This kept the metal somewhat agitated and no doubt was an important factor in hastening the decarburization 'process by the second method. Both methods gave satisfactory results as shown in Table 111. An interesting observation in connection with this 'work was that a small sample of carburized cobalt metal could be decarburized by heating it with an acetylene torch adjusted to give an oxidizing flame. This may have been due to the presence of carbon dioxide in the products of combustion. Samples of molten high carbon steel were decarburized by the same method and it is suggested that nickel and perhaps manganese can be decarburized in a similar manner. Additional work, including rate studies and other theoretical aspects of this problem, is in progress in this laboratory.

Jan 1, 1953

By R. W. Kraft, F. D. George, F. D. Lemkey

From a conszderation of the geometrically possible ways in which an array of lines or linear features in three-dimensional space can depart from a statistically random arrangement, a system was developed to describe and measure different types of anisotrypic arrangements of lines in opaque solids. The technique was applied to a specimen of unidirectionally solidified Al-Cwll, eutectic which contained microstructural imperfections termed lamellar faults. Experimental data obtained from photomicrographs of different facets of a grain of this alloy were then analyzed using this system. It was deduced that the defects, which are essentially linear in natuve, were predominantly parallel to one another but not parallel to the nominal growth direction probably because of some lateral heat flow during solidification. InGOTS of lamellar eutectic alloys which have been unidirectionally solidified under growth conditions which prevent colony formation consist of large elongated grains in which the lamellae are approximately parallel to one another. Deviations from a parallel lamellar structure within a grain are caused by extra lamellae which form occasionally during the solidification process. Three-dimensional analyses of such specimens have revealed that one extra platelet produces two defects, termed 1amellar faults, which can and do grow more or less independently of one another.' The faults are analogous in many ways to edge dislocations in crystals. If a lamella of one phase is considered to be basically two-dimensional, e.g., a surface, then a fault can be defined as the locus of points which delineates an edge (or half the periphery) of one extra lamella as it grows and forms bridges and saddles in an otherwise parallel arrangement oi lamellae, Fig. 1. Were it not for the fact that bridges and saddles occur in the structure, the extra platelet could be defined as the unit defect and the concept of linear faults of positive and negative character around the periphery of the extra platelet would be unnecessary. If an extra platelet is merely inserted (actually it is grown in) between other parallel platelets, the fault line around the periphery of the extra platelet would circumscribe one and only one platelet, namely the extra one, and the faults would lie in a plane parallel to the lamellae. But when an extra platelet merges with adjacent ones and each side grows independently of the other, it is no longer topologically possible to delineate "the extra plate." A fault circuit which either closes on itself or passes out of the specimen still occurs although it no longer will be coplanar with the lamellae. In fact, it is usually not even Planar even if the lamellae are. Under these conditions a concept that a specimen contains N extra platelets of a given size per unit volume would be very artificial and consequently meaningless. Therefore, because of the topological complexity of the alloys, it was deemed necessary to define one-dimensional

Jan 1, 1962

By Huey-Lin Luo, T. R. Anantharaman, William Klement

Two new metastable phases have been obtained in Au-Ge alloys by rapid cooling from the melt. One is of the hep structure with near-ideal axial ratio and may be considered a Hume-Rothery phase. The other has a complex tetragonal structure (a = 11.627Å and c = 22.191Å for the Au60Ge40 alloy) and may be looked upon as a superlattice made up of forty-four fee unit cells. Alloys with the tetragonal phase are charactevized by marked preferred orientation. The metastable constitution of the Au-Ge alloys is discussed with reference to the rate of cooling from the melt. THE Au-Ge equilibrium diagram features a rather deep eutectic near 27 at. pet Ge with a maximum solid solubility of 3.2 at. pet Ge in gold and is similar to the Ag-Ge, Ag-Si, and Au-Si diagrams.' The present study of the effects of rapid cooling from the melt on the structure of Au-Ge alloys constitutes an extension of similar investigations2-8 in this laboratory on alloys of noble metals with germanium and silicon. Nonequilibrium hep structures have so far been obtained by quenching Ag-Ge2, 3 and Ag-Si4, 5 alloys from the melt; an Au-Si alloy of approximately eutectic composition has been found6 to solidify in a noncrystalline state. EXPERIMENTAL PROCEDURES Twenty-nine alloys prepared from gold of 99.9+ pet and germaium of 99.999 + pet purity were investigated. The method of alloy preparation, the technique of rapid quenching from the melt, and the X-ray diffraction procedures were similar to those described previously.3, 4 Essentially, small sections (-20 mg) of thin alloy rods (-1 mm diam) were rapidly heated up to 1200°C in a graphite crucible under argon and the liquid alloy ejected by a helium blast onto a polished copper strip held on the inner periphery of a rotating wheel. The resulting thin foils were examined with or without the copper substrate in a G.E. X-ray Diffractometer or in a 114.6-cm-diam Debye-Scherrer camera. RESULTS Table I gives the constitution of liquid-quenched Au-Ge alloys, as estimated from intensities of X-ray reflections from the corresponding phases, viz., a (fee solid solution), ß (hep phase), ? (tetragonal phase), and diamond-cubic (dc) germanium. Despite unavoidable variations in the quenching rates, the proportions of the phases in different alloys were generally reproducible and stable at room temperature. There was no evidence of quenching strain, since the a doublets were well-resolved in high-angle Debye-Scherrer reflections in all cases except where stacking faults in the a fee and ß hep structures contributed to X-ray line broadening. The ß and ? metastable phases showed signs of decomposition to the equilibrium a phase and germanium only after a few hours annealing above 100°C. A few alloys around the eutectic composi-

Jan 1, 1965

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained-the isothermal growth of the phase follows a simple parabolic equation: [1 = ki [I]] where X is the thickness of the alloy layer, k the reaction rate constant, and [t] the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation: [k = Ae-QIRT [2]] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By A. E. Jenkins, A. Jostsons

Isothermal sections of the Ti-0-H phase diagvam at 600°, 700°, and 800°C have been constructed from equilibrium hydrogen pressure measurements over a range of Ti-0-H alloys containing up to 34 at. pct 0. Oxygen reduces the hydrogen solubility at fixed hydrogen pressure but increases the terminal solubility in the a solid solutions at the a/(a + P) phase boundary. Metal-lographic studies of alloys annealed below the eutectoid temperature show that oxygen also increases the ter-ninal solubility of hydrogen in the a solid solution in equilibrium with the hydride phase. The effect of oxygen on hydrogen solubility is discussed in terms of the electronic and geometric structure of interstitial solid solutions. THE isothermal solubility of hydrogen in a Ti-0 alloys at 800°C has been measured by Hepworth and ~chuhmann' who subsequently used ternary Gibbs-Duhem integrations to calculate oxygen activities in binary Ti-0 alloys. The present study aims to extend Hepworth and Schuhmann's measurements to alloys richer in oxygen and to a range of temperatures. This paper presents the results of hydrogen equilibrium pressure/concentration measurements in Ti-0 alloys as well as observations on the effect of oxygen on the terminal solubility of hydrogen in a titanium. The thermodynamic properties of binary Ti-0 alloys, derived from these measurements, will be published separately.' EXPERIMENTAL METHODS Specimen Preparation. Ti-0 alloys were prepared from iodide-refined titanium and titanium dioxide obtained by hydrolysis of redistilled titanium tetrachlo- ride. Specimens containing up to 16 at. pct 0 were prepared by electromagnetic levitation3 whereas a conventional tungsten arc furnace with a water-cooled copper hearth was used to melt oxygen-rich alloys. The specimen homogeneity was indicated by the constancy of lattice parameters of samples from various parts of the ingot as well as by the sharpness of the reflections on X-ray powder patterns. Oxygen-rich specimens in the composition range (20 to 34 at. pct), where ordering has been ~bserved,~ were annealed for 300 hr at 600°C prior to use in hydrogen solubility measurements. Apparatus. The hydrogen pressure/concentration measurements were made with a modified Sieverts apparatus shown diagrammatically in Fig. 1. Specimens were placed in a clear silica tube and impurity pickup by direct reaction with silica was prevented by lining the heated end of the silica tube with thin molybdenum sheet. A double silica tube was required to eliminate loss of hydrogen by diffusion through silica at high temperatures and high hydrogen pressures, the space between the tubes being maintained at a hydrogen pressure equal to that above the specimen. Hydrogen was purified by diffusion through a Ag-Pd tube.= Hydrogen pressures were measured with a mercury McLeod gage in the range 0.001 to 4 Torr

Jan 1, 1968

Jan 1, 1942

I HAVE previously shown you in the Fifth Book the process of making guns and gun carriages, together with other preparations and methods of moving them. If I now failed to show you more about them, it would be as if I had pointed out only the useless shadow of a thing, for I did not show the kinds and arrangement of their supplies or how the effects for which they are made are achieved. For these reasons I now wish to tell you, in addition to what I have already said, how saltpeter is made and the methods of refining it well; what it is and how without it guns and many effects of violent and artificial fires would have been discovered in vain. After this, I also wish to tell you the methods of compounding the powders for large and small guns, and finally how these are loaded and discharged. I also wish to tell you how mines are made, and fire tubes, [149v] fire pots, squibs, fireballs, rockets, shells, grapeshot, and other similar devices for shooting fire in order to bum ships, supplies, bridges, and ramparts, or, in offense, for firing on batteries. I also wish to teach you to make certain bronze balls for shooting, which carry fire and break in many pieces when they hit. For surely, besides being terrifying to the sight, they would be harmful to armies lined up in battle when they are fighting. Likewise, I wish, to enlighten you as to how artificial fires are made that last long and are difficult to extinguish. Since these are fine and useful things in wars, every captain and soldier should give them consideration and know how to use them when necessary. You will be pleased to have this information if for no other reason than that you can teach it to those who take delight in celebrating holidays with festivities and with fires.

Jan 1, 1942