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By C. C. Merrill

Studies were made to determine the amenability of yttrium to fused-salt electrorefining in a controlled atmosphere. Tests were conducted in a LiCl- YCl3 electrolyte system at 710° C. The major variables studied were the YCl3 content of the electrolyte, from l.7 to 13.4 mol percent, and the initial cathode current density, from 410 to 1,630 amperes per square foot. Vacuum distillation was employed to remove salt from the deposited metal. Metallic impurities, except for lithium, could be reduced to near or below their lower analytical limits, ranging from 10 ppm for Cu to 300 ppm for Ta; reduction of oxygen content, however, was accomplished only in metal produced from electrolytes with 5.4 mol percent YCl3 or less. Initial cathode current density had little effect on the purity of the product.

Jan 1, 1967

By Charles S. Allbright

This report describes hydrogenation of petroleum distillate fuels in bench scale equipment and the effects of hydrogenation on the storage stability and the composition of the fuels. Two distillate fuels were hydrogenated in laboratory equipment using a commercially available cobalt molybdate catalyst. Reactor temperatures were varied from 600° to 850° F and pressures from 100 to 600 psig. Product fuels were analyzed by ASTM, Bureau of Mines, mass, and infrared methods. Hydrogenation of a catalytically cracked fuel from Oklahoma crude oil significantly improved the storage stability, reducing insoluble gum formed during 9 months of storage at 110° F from 19.0 to 1.3 mg per 100 ml fuel, average. Conversion of the olefins to other hydrocarbon types varied with the temperature of hydrogenation--at 700° to 850° F the conversion was mainly to aromatics, at 650° F about 50:50 to saturates and aromatics, at 600° F principally to saturates. Processing a fuel composed of a mixture of virgin distillate and catalytically cracked stock, both from Illinois crude, at 700° F and 200 psig effected marked improvement in stability; the buildup of insoluble gum in storage was lowered from 18.3 to less than 1 mg per 100 ml fuel.

Jan 1, 1967

By R. A. Guereco

Accurate measurements of physical dimensions of a section of stainless steel capillary tubing are presented and used to develop two final working equations for an absolute gas viscosimeter. The effects of pressure and temperature on these dimensions are considered. The internal surface finish and nonuniformity of the capillary bore are discussed, as well as entrance, kinetic energy, gas slippage, and gas compressibility correction factors.

Jan 1, 1967

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By M. Khorouzan, L. Thomas

Designers of semiconductor devices have been strivi,ng to resolve problems associated with Au-A1 alloys in bonded in.tercomzeclions. One approach now being- used is that of waintaining a physical seyav-atioz between the two metals in bond areas. This is accolrzplished by alunzincnz-plating a bonding area on the tips oJ the kovar leads and using alcminurn wires to join the senzicondictor device to the leads. The portion of the kovar lead which is on the externul side of the sealed package is gold-plated to provide an oxide-free surface for soldering or welding. A discoloration condition originally thought to be sinilar to purple plague, occuving in the yluled uluninur bonding area after package sealing, has been investigated to determine its efiects ipm bond integrity. Electron-micro-probe analysis determined that no1 only gold, but lead, zinc, and silicon were also present in the discolored area. A series of samples conlaining' conkrolled umonts of these inzpitrities weve prepared and subjected to a sil.zuluted sealing process. The investigations swcued that, of the contawiinants, only zinc toas detrinenlul to Lhe bond integily. The discoloration condition itself was found not to be detrimental to the bond integrity. DESIGNERS of semiconductor devices have been striving to resolve problems associated with Au-A1 alloys in bonded interconnections. One approach now being used is that of maintaining a physical separation between the two metals in bond areas. This is accomplished by aluminum plating a bonding area on the tips of the kovar leads and using aluminum wires to join the semiconductor device to the kovar leads. The portion of the kovar lead which is on the external side of the sealed package is gold-plated to provide an oxide-free surface for soldering or welding. Contamination as evidenced by discoloration of the aluminum-plated area was observed in a number of integrated circuits undergoing examination for defect characteristics which cause electrical failures.' This paper contains the results of an investigation to determine the nature of this discoloration, its cause, and its effect upon the integrity of the interconnection bond. I) THE NATURE AND EXTENT OF ALUMINUM-BOND CONTAMINATION The initial hypothesis in the investigation was that the discoloration was caused by reaction of the aluminum film with some unknown contaminants during the sealing of the hermetically sealed integrated-circuit flat package. The package is a rectangular ceramic container sealed with glass which surrounds the kovar leads as well as joining the top to the bottom. The seal is made hermetic by heating and cooling the package to devitrify the glass. In the case of the packages under investigation, the hermetic sealing had been accomplished with dry air as internal atmosphere. The apparent effect of contaminations as observed by microscopic examination was the formation of surface oxides having variations in color encompassing the whole spectrum of visible light. The contamination appeared to be related to one of the more notorious examples of these colorations, the so called purple plague.' In addition to purple plague, Fig. 1 shows the tarnish in the luster of the aluminized surface in the bond area which had been observed in many of the integrated circuits. To identify the contaminant in the bond area electron-probe microanalysis techniques were used.3 Fig. 2 shows the result of this analysis. The contaminants identified were gold, aluminum, zinc, lead, silicon, and cobalt. Fig. 2(a) is a back-scatter display of the area under study. The back-scattered electrons provide a general indication of the distribution of elements in the specimen surface. Elements with higher atomic number scatter more electrons back from the surface and are seen as light areas in the picture. The sample current, Fig. 2(b), is the amount of current conducted by the specimen as a result of electron-beam striking it and is an indication of element distribution. The Sample current is the reverse of back-scatter and complements it. Other pictures in Fig. 2 are produced by characteristic X-rays generated by the elements, allowing the isolation of the element of interest. The isolated element appears white and all other elements are dark. In this manner a comparative study provides a correlation between different surface areas and the elements which are in these areas. The area covered by the gold film, Fig. 2(c), shows that the boundary between the gold film and the kovar is not sharp as expected and that some sort of diffusion has taken place. Fig. 2(c) shows that some gold particles have been carried to the bond area and are in the proximity of the bonded wire in spite of the presence of a physical barrier in the form of the un-

Jan 1, 1967

By A. W. Deurbrouck

This Bureau of Mines report describes the preparation characteristics of the significant coalbeds from which samples could be obtained in Upshur County, W. Va. One of the 14 samples collected was of metallurgical quality as received, 6 could be sufficiently upgraded to provide acceptable products, and 7 could not be upgraded to metallurgical quality because of their high sulfur contents.

Jan 1, 1967

By D. K. Deardorff

The purpose of this work was to investigate the hafnium-carbon phase diagram. Alloys used to study this system were prepared from high-purity components by both consumable-and nonconsumable-electrode arc melting. Data for the diagram were obtained on the alloys by metallography, optical pyrometry, thermal analysis, heat treatment, and X-ray diffraction. The data indicate that a carbide compound occurs over considerable range of composition, and that one of each of the following types of reactions occurs in the hafnium-carbon system: Peritectoid, peritectic, and eutectic. The maximum melting temperature of hafnium carbide is 3,840° C at 49 to 50 atomic percent carbon, and the composition range of hafnium carbide at temperatures of 2,150° to 2,380° C is from 37.0 to 48.5 atomic percent carbon. The hafnium a-S transformation temperature is raised on alloying with carbon from 1,750° to 1,890° C, where a peritectoid reaction isotherm occurs. Alloying hafnium with carbon increases the hafnium melting temperature from 2,190° to 2,250° C, at which temperature a peritectic reaction occurs. Hafnium carbide and carbon react at 3,055° C to form a eutectic of 68.3 atomic percent carbon.

Jan 1, 1967

By W. E. Anable

The Bureau of Mines studied the purification of commercially available vanadium in the 100-kw electron-beam furnace. Purification studies were conducted on a 100-gram button scale by melting and holding the liquid vanadium at temperatures ranging from 2,060° to 2,080° C at pressure of 5(10)-5 torr for periods ranging from 5 to 20 minutes. The effect of doping vanadium with carbon and metallic additions was determined. This study demonstrated that hydrogen was readily removed to 3 ppm or less, oxygen and carbon were reduced to less than 100 ppm each, and the metallic impurities were reduced Co the range of 10 to 500 ppm. The nitrogen content was not reduced in any of the buttons; rather, the nitrogen concentration generally increased as samples were held for successively longer periods. Oxygen was removed much faster and more completely when vanadium was doped with small carbon additions or one of several dopes prior to melting.

Jan 1, 1967

By Richard N. Spencer

Electric-furnace smelting for simultaneous recovery of zinc spelter and lead bullion from complex lead-zinc sinter was investigated. Reduction of lead and zinc was satisfactory. Condensation of lead and zinc vapor to pyrophoric metal powder in a water-cooled, shock-condensing system produced excellent recoveries. Metal-splash condensation to produce zinc spelter was unsatisfactory. Special smelting experiments differentiated the effects of several smelting parameters on zinc metal recovery. The principal cause for unsatisfactory zinc metal recovery was transfer of iron to the condenser and subsequent degradation of zinc in a mixture composed of lead and an iron-zinc intermetallic compound. Limitations of the process were determined. Slag-resistance open-bath electric smelting of complex lead-zinc sinter is not considered feasible.

Jan 1, 1967

By Ronald P. Hollenbeck

This study reviews and discusses the fluorspar industry in the Eastern United States, with emphasis on factors controlling the industry such as production, consumption, uses, and transportation. The greatest potential for increased consumption of fluorspar in the immediate future was found to be in the manufacture of fluorine chemicals and steel. Important factors affecting the future domestic industry include imports and the maintenance of adequate domestic fluorspar reserves. Exploration, commercial deposits, mining and milling, reserves, and new developments in the industry are covered.

Jan 1, 1967

By K. Sassa, I. Ito

The dynamic principal stresses induced within rock by an explosion under con fined conditions are analyzed for the case of blasting with one free face by applying the values of measured radial displacement, particle velocity and so on to equations derived from the theory of elasticity. The dynamic stresses on the free face are also calculated from the strain measured by wire strain gauges affixed on the free face. Some results obtained are briefly: 1) The maximum stress on the free face appeared at the intersection between the free face and the burden, and its magnitude was about twice as large as the magnitude of the tangential tensile stress imparted by the incident stress wave within the range related to the breakage by blasting. 2) The maximum value of the compressive stress near the free face was decreased due to the existence of the free face, while that of the tensile stress was increased. 3) At any point near the free face, the directions of the principal stresses in the r? plane using spherical coordinates with the origin at the center of the spherical charge, changed with time except in the direction of the burden. However, at another point near the explosion point where the principal stresses were mainly those stresses caused by the initial longitudinal wave, the directions of the principal stresses coincided with those of the coordinate used. 4) The maximum value of the tensile stress in the F direction was larger than those in the re plane at and near the free face. 5) The tensile stress caused by the Hopkinson effect appeared only near the burden. 6) It is presumed from the results of stress analysis that radial cracks will be produced in the rock mass near an explosion point, but with the approach of the free face, the directions of cracks curve towards a direction parallel to the free face. INTRODUCTION In order to investigate the mechanism of rock breakage by blasting, it is considered to be very im- portant to know how the stresses are generated and distributed within the rock by explosion of a confined charge. As part of a research program concerning the mechanism of rock breakage by blasting, the authors have already published papers on the detonation pressure produced at the inner surface of the charge hole1 and on the behavior of the dynamic stresses within rock caused by an explosion in the case where no free face existed.' In this study the dynamic stresses on and near the free face have been investigated for the case of blasting with one free face. The mechanism of rock breakage in blasting is discussed in the light of these studies.

Jan 1, 1967

By H. A. Gorrell, S. R. L. Harding

"The potash beds in the Saskatchewan portion of the Williston Basin occur in the upper portion of the Prairie Evaporite formation of the Devonian Elk Point Group. They represent the late stage of a major evaporitic cycle. Two other evaporitic cycles are known in overlying beds, but these apparently never reached the stage of potash salt deposition. The basin in which salt deposition took place extended from the northwestern corner of Alberta southeastward across Saskatchewan into Manitoba, North Dakota and Montana. Deposition of potash salts was apparently restricted to the southeastern portion of the evaporite basin. On a regional basis, five major stratigraphie divisions of the potash-bearing strata have been made. Locally, several of these units may be divided into correlatable sub-units. The potash-bearing strata are separated and overlain by predominantly halite layers of varying thickness. Cross sections show the regional correlation of the potash-rich zones, and maps show the present distribution of the individual potash-bearing zones and the areas of richer development for each zone. The maps tend to substantiate the interpretation of considerable subsurface solution of salt and potash beds."

Jan 1, 1967

By H. E. Powell

Magnetic susceptibilities were determined by the Bureau of Mines fur 19 cobalt- and nickel-bearing minerals and for a suite for synthetic cobalt-nickel diarsenides analogous to the rammelsbergite and safflorite series. Relations between susceptibility and composition were found to be nonlinear for both impure natural minerals and pure synthetics.

Jan 1, 1967

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

By Robert E. Wood

The compressibility factors, Z, of helium, nitrogen, and helium-nitrogen mixtures in the three-dimensional space of temperature, pressure, and gas composition have been related to the Leiden form of the virial equation of state. The dependency of virial coefficients through the fifth on temperature and gas composition has been established for the temperature range 133.15° to 748.15° K. Compressibility factors, Z, have been computed from the equation of state and tabulated as functions of gas composition, pressure, and temperature. Tabular values of Z are presented for 30.00 through 100.00 percent helium for temperatures from 240° through 700° R for pressures from 14.696 through 3,050 psia and for temperatures from 720° through 1,300° R for pressures from 14.696 through 1,500 psia. Tabular values of Z are presented at increments of 5.00 percent helium and 20° R, and, for pressures greater than 50 psia, at increments of 50 psi.

Jan 1, 1967

By James A. L. White

Although the quantity of native sulphur associated with volcanism is large, production from such deposits represents only a very small percentage of total world production, This paper describes the location of the known deposits, the typical geology of these deposits and the nature of the sulphur mineralization. Methods of treatment are discussed and some comments are offered on the economic position of these occurences in world sulphur markets.

Jan 1, 1967

By H. G. Warren, E. W. Hough

Correlation of interfacial tension of the methane-n-pentane and methane-n-decane systems was made by Hough and Stegemeier by the use of the Weinaug and Katz equation. The methane-n-heptane and ethylene-n-heptane systems were investigated by the authors. Additional systems taken from the literature were the me thane-propane system by Weinaug. and Katz, the methane-n-butane system by Pennington and Hough, and the n- butane -carbon dioxide system by Brauer and Hough. These systems were analyzed by the Weinaug-Katz equation and the Sugden equation on the IBM 1620 11 computer using a regression analysis program. Parachor and exponent values for each component and system were determined. The experimental work was close to the critical point of the light component in the n-butane-carbon dioxide and ethylene-n-heptane systems, between the critical points of the light and heavy components in the methane-n-pentane, methane-n-heptane and methane-n-decane systems, and close to the critical point of the heavy component in the methane-pmpane and methane-n-butane systems. An empirical formula was developed to find a value of the constant B in the Sugden equation for binary hydrocarbon systems from the parachor values of the two components. Interfacial tension for binary hydrocarbon systems was found to be a direct function of liquid-vapor phase density difference in the same manner as a single-component system. DISCUSSION Interfacial tension may be defined as the measure of the specific free surface energy between two phases having different compositions.1 The interfacial tension (IFT) for a binary system may be predicted for any temperature and pressure if the

Jan 1, 1967

By W. S. Landers

Nine high-volatile bituminous Utah coals were carbonized singly and in blends with low-and medium-volatile bituminous coals. Of the 9 coals, 2 are in commercial use as the base coals in blends that produce industrially accept-able metallurgical coke, while 7 are regarded as weakly coking and are not used commercially in coking blends. The carbonization tests were made in a la-inch diameter, cylindrical retort, using 50-pound charges. Sunnyside coal blended with autogenous char generally produced larger and stronger coke than was yielded by straight Sunnyside coal. The volatile matter of the char and the concentration of the char in the blend appear to be important parameters influencing coke size and strength. A blend of 10 per-cent autogenous char of 7.2-percent volatile matter with Sunnyside coal yielded coke that was larger, stronger, and of higher apparent specific gravity than coke produced from an industrial coke oven blend consisting of 15 percent medium-volatile coal and 85 percent Sunnyside coal.

Jan 1, 1967

By Donald P. MacKinnon

"This paper is a commentary on selected trends within the transportation industry.In general, innovations are taking place within all modes of transport (road, rail and water) serving the industrial minerals industry which will affect future distribution patterns, methods and costs. Significant technical innovations in the transportation of solids by• pipeline will also appear, perhaps in the near future, permitting the transport of specific commodities, including some industrial minerals. However, the timing and magnitude of the commercial exploitation of solids pipelines are heavily dictated by marketing factors and distribution system logistics, as well as by the innovations likely to take place within competitive modes of transport. Competitive technological developments will include increased ship capacities, improved bulk-handling facilities, larger and specialized bulk-handling rail equipment, unit trains, containerization, larger ""off-highway"" vehicles and greater inter-modal integration. Equally significant are some ""soft-ware"" techniques such as the growing interest in total distribution cost concepts. However, the impact of the developments will not be spread uniformly over all Canadian industrial minerals."

Jan 1, 1967

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of 'composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert's-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.' The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967