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By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By G. A. Gross

"The Soviet Union has enormous reserves of iron ore in many different kinds of deposits that are widely distributed in this vast land area. The present iron ore industry is based mainly on deposits in Precambrian cherty iron-formation at Krivoy Rog, Kursk and Murmansk. Extensive reserves of both naturally enriched hematite ore and magnetite iron-formation in these areas alone could sup-ply all the domestic ore required for several hundred years.Many contact metasomatic magnetite deposits discovery in recent years in the eastern Ural Mountain belt and east of the Kusnetsov basin in Siberia are being developed, with ore reserves measured in billions of tons. Oolitic limonite-chamosite-siderite ores of Cretaceous and younger age at Kerch on the Black Sea and around the east and southern perimeter of the West Siberian basin constitute some of the largest concentrations of iron in the world. These sedimentary ores are low grade, of poor quality and difficult to beneficiate. Banded jasper magnetite and hematite iron-formation in volcanic rocks of Devonian age in Kazakhstan and along the Mongolian border are of special geoloica1 significance.Iron deposits in the Krivoy Rog and Kursk areas were examined and a large number of geologists discussed their work on deposits in many other parts of the Soviet Union during the writer's seven-week study tour of mines and research institutes in Moscow, Leningrad, Novosibirsk in Siberia and Kiev in the Ukraine. The descriptive geology of iron deposits of useable ore and of marginal material has been well documented in the course of systematic work and a large number of scientists are studying fundamental problems on the origin and treatment of iron ore."

Jan 1, 1967

By R. T. Sorensen

Bench-scale and continuous testing were performed to adapt the anionic process for flotation of calcium activated silica to the fine-grained hematitic-goethitic jaspers from the Marquette range, Michigan. These ores typically contain about 35 percent Fe and require grinding to about 80 to 100 percent minus 400 mesh to insure an adequate liberation of gangue from the iron oxides. A method for removal of troublesome slime fractions without excessive iron loss, by first dispersing the quartz and then selectively flocculating the iron oxides, was evolved in the laboratory and successfully accommodated to pilot plant practice. The efficiency of the flotation process was improved with respect to both reagent usage and concentrate grade and recovery by using the selective flocculation-desliming technique as a pretreatment. The benefits of the combined desliming-flotation procedure were most evident in pilot plant processing. The best tests on two ores yielded recoveries of about 84 percent in concentrates containing 65.1 percent Fe and 4.8 percent SiO2 and 66.2 percent Fe and 3.9 percent SiO2, respectively. These results are in comparison to recoveries about 10 percent lower than the above to concentrates containing 63.9 percent Fe and 6.6 percent SiO2 in the one instance, and 63.6 percent Fe and 7.2 percent SiO2 in the other, obtained by flotation without the prior desliming treatment.

Jan 1, 1967

By L. N. Cosner, C. F. Austin, J. K. Pringle

Shock wave attenuation studies with three igneous rocks are reported: a spessartite elastic to low intensity stress waves, a diorite which is anelastic, and a porous scoria. The level of shock passing through a given thickness of rock has been determined by donor-receptor methods using high speed streak cameras. Test results include shock propagation velocities adjacent to the explosive, the dependence of test results upon test geometry, and the variation in shock wave attenuation in these three common igneous rock fabrics. The utilization of explosives in rock mediums involves a series of interrelated phenomena. These are the detonation process within the explosive, the transfer of energy from the explosion products to the surrounding rock medium in the form of sound or shock waves, and the transmission of the resulting waves through the rock medium to create damage in the rock mass. The subject of this paper is the investigation of the close-in phenomena that occur in the intensely shocked rock immediately adjacent to a detonating explosive charge. The specific aspects studied include propagation velocities, free surface velocities, pulse attenuations and the determination of the equations of state for the test rocks employed. In addition, a series of tests was conducted to indicate the dependence of the test results on the charge diameter utilized. The equations of state for rock materials have been investigated by a number of authors. Lombard, ',' Grine and Fowles,3,4 Zharkov, 5 Hughes and McQueen,6 Chabai,7,8 and Bass9 have published equation of state data on rock materials similar in structure or composition to those investigated in the study. Rinehart10 has prepared a voluminous tabulation of the available equation of state data from these publications and in addition has included data on many other rock and earth materials in his compilation. The reader is referred to the extensive tabulations and bibliography of Rinehart for classical studies involving the equations of state of metals and other solids and liquids. The problems of sympathetic detonation between drill holes in hard rock environments has received the attention of various authors as have the problems of explosive rock coupling close-in stress wave attenuation and explosive diameter effects. 11 to 18 In particular, the don or-receptor geometry of this report is very similar to the geometry of adjacent drill holes in rock. Most published pulse velocity and attenuation work in rock has been devoted to velocities at much lower amplitudes than those associated with close-in explosives phenomena and most attenuation studies involve transmission and attenuation across large spans of material. Excellent work in these areas has been published by the U. S. Bureau of Mines and by many individuals and groups engaged in geophysical research. SELECTION OF TEST MATERIALS A series of rock materials was desired for this test program that would be meaningful industrially, and that would also yield comparative results from a research viewpoint. Based on the availability of a series of related petro-fabrics, for which there is an abundance of physical and shock response data, three igneous rocks were selected as the test series. The applicability of shock wave studies in igneous rocks to industrial problems is readily demonstrated. Hardrock tunneling, quarrying and mining take place in igneous rocks throughout the world. From a research point of view, igneous rocks exhibit a wide variety of grain sizes and considerable diversity in composition, yet the common igneous rocks have a general similarity in their constituent mineral structures and in their grain-to-grain bonding mechanisms. The latter is based on the concept of rock formation through magma cooling and crystallization, though the degree of liquefaction in granitic plutonic masses is indeed a moot question. Three specific types of igneous rock were chosen for study. A coarse-grained granitic textured rock was desired that would serve as a representative of the widely abundant intrusive rocks of the world and

Jan 1, 1967

By R. W. Boyle

"The concept of using chemical methods in prospecting dates back at least to the middle of the 16th century. Modern methods of geochemical prospecting, however, based on secondary haloes and utilizing trace-element techniques, were first practised in the U.S.S.R. and the Scandinavian countries in the 1930's. After 1945, methods based on soils, stream sediments and vegetation were rapidly developed in the U.S.A., the United Kingdom, Canada, France and other countries.The modern methods of geochemical prospecting owe their rapid development in the 20th century to the following:1.-Recognition of the primary and secondary dispersion haloes and trains that are associated with all mineral deposits. 2.-Development of accurate and rapid analytical methods utilizing the spectrograph and the various specific sensitive colorimetrie reagents, especially dithizone. 3.-Development of polyethylene laboratory ware of all types and the development of resins. This permitted greater freedom of field analyses and reduced the incidence of contamination.4.-Development of gas chromatography. This permitted the rapid and accurate determination of hydrocarbons in petroleum prospecting.Future research in geochemical prospecting should be focused on the following tasks: 1.-Definition of geochemical provinces and their relation to mineral deposits. 2.-Development of methods for discovering large low-grade deposits. 3.-Development of methods for discovering deeply buried deposits. 4.-Further development of methods to outline primary haloes. 5.-Eiucidation and formulation of techniques to relate the size and intensity of anomalies to the grade of the deposits. 6.-Development and refinement of biogeochemical methods, especially those based on indicator plants, chlorotic or toxic effects, and microbiological techniques. 7.-Definition of the types of primary and secondary haloes associated with accumulations of oil and gas."

Jan 1, 1967

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By G. E. Wittur

"The twenty-one members of the Organization for Economic Cooperation and Development, comprising eighteen western European nations plus Canada, the United States and Japan. account for two-thirds of world steel production. The Special Committee for Iron and Steel was formed by the OECD to study trends and problems in the steel industries of member countries. The paper begins with a summary on the Organization, including an historical sketch, its structure, member-ship and objectives. The steel industry of the entire OECD is briefly described before proceeding to a more detailed discussion of various aspects of the steel industries of European OECD members, emphasizing practices and conditions that differ from those in North America. Benefits to Canada of representation at meetings of the OECD Special Committee for Iron and Steel are described."

Jan 1, 1967

By M. C. Makepeace

"It is the objective of designed experiments to obtain more information for less material and process cost than can be obtained by traditional experimentation. In this paper, the fundamental concepts on which the statistical design of experiments is based are briefly re-viewed according to the following outline: The Experiment The Design The Analysis Two simple 2"" factorial experiments are presented as examples."

Jan 1, 1967

By Bernard Porter

The rate of the heterogeneous reaction between reactor-grade yttrium and lithium fluoride in lithium fluoride-yttrium fluoride mixtures was measured using a quartz spring balance. At 950° C the magnitude of the rate of reaction is 10-5 grams of yttrium/cm2-sec. The heat of activation for the reaction is 38.3 kilocalories per mole of LiF. A surface-controlled mechanism is proposed in which LiF is adsorbed on the yttrium metal surface. An activated complex is formed when additional LiF reacts with the adsorbed LiF-metal site. The activated complex then decomposes to the products) which are lithium metal and YF3. The importance of the reaction in the electrowinning of yttrium metal from fluoride electrolytes is discussed.

Jan 1, 1967

By A. Balint

The Photometric Optical Separation process is introduced and examples of sorting machines are given. Applications of the process are outlined in general terms with reference to specific types of industrial installations. Brief description is given of the capabilities and limitations of available equipment, including cost estimates.

Jan 1, 1967

By John S. Berber

To improve the economics of low-temperature carbonization of coal, the Bureau of Mines is conducting research on the upgrading of the product tar to marketable chemicals. This report describes experiments on the catalytic hydrodealkylation, followed by catalytic vapor-phase oxidation of the dealkylate to phthalic and maleic anhydrides, of mixed residues from the urea adduction of lignite-neutral oil fraction and on the catalytic thermal dealkylation of high-boiling tar acids. The hydrodealkylation experiments were conducted at pressures from 1,000 to 1,750 psig and at temperatures from 600° to 1,000° F. The oxidation was, in all cases, at atmospheric pressure and 9500 F. Maximum yield of maleic anhydride, based on the liquid feed to the hydrodealky1ation unit, was 12.2 percent at 750° F and 1,500 psig; that of phthalic anhydirde was 6.9 percent at 650° F and 1,500 psig. Maximum yield of combined anhydrides was 18.8 percent at 650° F and 1,500 psig. The non-dealkylated feed material, upon oxidation, yielded 8.9 percent and 3.8 percent maleic anhydride and phthalic anhydride, respectively.

Jan 1, 1967

By Joseph M. Singer

Having established that sodium chloride reduces the incendivity of explosives, the Bureau of Mines studied the effect of sodium nitrate in reducing ignition hazards. Gallery experiments showed that sodium nitrate reduced the incendivity of certain explosives to 8 percent natural gas in air but increased their incendivity to coal dust predispersed in air. Laboratory experiments using hot jets from explosions of stoichiometric mixtures of methane-oxygen-nitrogen showed that both sodium chloride and sodium nitrate reduced the incendivity to methane, to mixtures of coal dust and methane) and to coal dust. The difference between the gallery and laboratory results with respect to coal dust is attributed to temperature-time effects.

Jan 1, 1967

By L. A. Neumeier

A refinement of the tungsten-cobalt phase diagram is presented for compositions to 85 at. pct cobalt and for temperatures to the solidus. Preparation of alloys by powder metallurgy methods is described, and the results of studies made by a combination of techniques involving microscopy, X-ray diffraction, thermal analysis, and dilatometry are discussed. The existence of u-W6Co7 is confirmed (rhombohedral D85 structure). The W6Co7 phase forms periectically at 1,685'115° C by reaction of liquid with primary W; the peritectic melt is at 71 at. pct cobalt. The homogeneity range of u-W6Co7 extends to both sides of the ideal stoichiometric ratio, through a compositional range of about 5 at. pct. The compositional limits for u-W6Co7 vary slightly below 1,471°±5° C, the temperature of the eutectic reaction forming u-W6Co7 plus a. The eutectic composition is at 79 at, pct cobalt. The existence of WCo3 is confirmed (hexagonal D019 structure). WCo3 forms peritectoidally at 1,093°±5° C by reaction between a and u-W6Co7 and exists over a narrow homogeneity range of 0.5 to 0.6 at. pct. The solid solubility of cobalt in tungsten is low (maximum 0,9 at, pct cobalt) and results in contraction of the tungsten lattice. Tungsten is extensively soluble in a-Co at higher temperatures; the a-Co lattice is expanded by the presence of tungsten in solid solution. There was no indication of the formation of a o-phase nor of any intermediate phases other than WeCo7 and WCo3. The WeCo7 and WCo3 phases are compared with similar phases in other systems.

Jan 1, 1967

By R. E. Lindstrom

The mineral bastnasite is utilized to describe alternate processes for the extraction and separation of the rare-earth elements by solvent extraction. The rare earths can be acid-leached directly or fused with NaOH before acid leaching. Cerium, the major constituent, can be recovered by fractional precipitation, fractional leaching, or solvent extraction with tri-nbutyl phosphate. The latter process is capable of producing 99.5-percent pure CeO2 at 98+ percent recovery. Lanthanum is subsequently recovered by fractional precipitation or solvent extraction with a nitrogen-based extractant. A 20-stage mixer-settler operation with a primary amine extractant results in a 95-percent pure La203 fraction at 96 percent recovery. Europium is amenable to extraction from most of the remaining rare earths with an organophosphate extractant. Selective stripping of the europium, followed by reductive precipitation, produces high-purity Eu203. Another possibility for europium purification involves the differential extraction of europium with an amine followed by a sub- sequent reducing strip. Separation of the remaining elements is more difficult but can be accomplished with amine or quaternary ammonium extracts. Typical separation factors achieved are 3. 8 for praseodymium-neodymium and 10. 5 for neodymium-samarium.

Jan 1, 1967

By Leo A. Schrider

A prediction for oil recovery from a pilot waterflood in the Kane oil- field, located in Elk, Forest, and McKean Counties, Pa., was made and compared to actual field performance. Water-injection and production histories, well logs, other field data, and results from laboratory tests of core material were used in this analysis. Performance of the pilot waterflood, initiated in January 1963, was predicted using a modified Craig, Geffen, and Morse calculation technique. Maximum recovery from this low permeable, preferentially oil-wet formation was predicted to be about 22,500 barrels of oil after 300,000 barrels of water had been injected into the pilot waterflood area. After additional field data were collected it became necessary to reevaluate the pilot waterflood area. The gas saturation prior to the waterflood was estimated to have been 20 percent, based on an assumption regarding the required volume of water injected to initiate oil production. In view of the actual field performance, a gas saturation of 13 percent is indicated. When this gas saturation and the method originally proposed by Craig and others are used) the predicted results are more representative. In December 1965, field performance was further analyzed using a hyperbolic-decline curve as presented by Arps. Based upon this evaluation method, the pilot water flood in the Kane sand should produce 37,000 to 42,000 barrels of oil with the injection of 300,000 barrels of water into the pattern. By continuing this secondary-recovery project to a reasonable economic limit, ultimate oil recovery may be as much as 50,000 to 55,000 barrels, or 129 to 142 barrels per acre-foot from 36.5 acres.

Jan 1, 1967

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting' thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts' method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s'- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts' apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts' method was used for this study and followed the procedures outlined previously.l' The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts' law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts' law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van't Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,' and Humbert and 1liott.l' The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i'- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967

By R. F. Waters

Laboratory-scale selective volatilization methods developed by the Bureau of Mines to recover germanium and gallium concentrates from coal fly ash and phosphorus furnace flue dust are summarized. In the better experiments between 85 and 98 percent of the germanium was recovered as the lower oxide and as sulfides, and between 75 and 97 percent of the gallium was recovered as the lower oxide and as the trichloride. Grades of the condensates were inconsistent and varied between a few tenths of a percent and 8 percent, depending on the method used. In the primary extractions of germanium alone the degree of enrichment surpassed 100 to 1, and for gallium the best ratio was 30 to 1. Upgrading of condensates by vaporization retreatment and by leaching and precipitation is discussed. An appreciable degree of mechanical preconcentration by attrition scrubbing and elutriation was possible on two fly ash samples.

Jan 1, 1967

By Roger V. Pierce

"WITHOUT mineral wealth, modern man would not exist. True, man could survive on a stone-age basis with an average life expectancy of, say, 25 to 30 years -once he got past infancy.However, no metal would tip his arrow in a hunt for protein; no steel plough would break the soil for the organized planting of seed; and no coal, nor oil, nor natural gas nor uranium fuels would pro-vide him with light or beat or safety from either beasts, or other men, or an unkind nature that threatened him and his family.Modern agriculture, fishing and forestry represent the other three wealth-producing industries. With-out metals, non-metallics and energy minerals, however, it would be impossible to fit any of these to man's modern needs."

Jan 1, 1967