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By E. J. Rapperport, J. P. Pemsler

Proton irradiation of high-purity distilled berylliuwz was utilized to introduce various hydrogen contents from 0.00075 to 0.075 at. pct (0.83 to 83 ppm) in a band 0.004 cm wide. After irradiation, the specimens were heat-treated to effect hydrogen agglomeration. Observations of agglomerates in all specimens of the lowest hydrogen content indicate a hydrogen solubility of less than 0.83 ppm in the temperature range 350" to 1050°C. Estimates of the inter diffusion coefficient in the hydrogen solid solution of beryllium were obtained from measurements of the dimensions of hydrogen-depleted zones survounding agglomerated bubbles. A value of (approximately) 3 xlo-' sq cm per sec is obtained for the diffusion coefficient at 850" to 900°C. PREVIOUS investigators found that We solubility of hydrogen in beryllium is very small. Gulbransen and Andrew' state that beryllium does not react with hydrogen at 23 mm Hg between 300" and 900°C. Cotter ill et a1.' report that as-machined beryllium has an adsorbed hydrogen layer of 0.007 cu cm per sq cm of surface. No additional hydrogen is picked up in hydrogen at 0.1 mm Hg and between 200" and 80O°C, or when hydrogen is bubbled through molten beryllium. Beryllium hydride has been reported to exist in an ether solution,394 but decomposes at about 200°C; there is no substantial evidence for the existence of the hydride in the solid phase.

Jan 1, 1964

By ALEX. S. THOMAS

HOWEVER good a furnace may be in regard to design, etc., or however excellent in the quality of the gas used, a suitable heat for the successful working of the metal cannot be obtained unless the melt be coated with a proper quantity of slag. This coating may be excessive or it may be deficient in quantity. The right degree of heat is the essential condition of successful working, for the quality of the steel made is never very good when the metal is allowed to simmer in the furnace for an excessive period, and this heat cannot be obtained if the metal is not protected by a proper covering of slag. This is not only to prevent the metal being over-oxidized and wasted, but also to prevent the metal being chilled when exposed with only a thin covering of slag. The slag may be obtained in either of two ways : 1, naturally, by the presence of sufficient silicon in the iron used, to unite with iron oxide to form a staple slag ; or, 2, by the addition of slag or free silica. In the first case the slag is formed naturally by the action of the oxygen in the flame - i.e., the oxidizing atmosphere of the furnace-on the silicon in the metal when melting. The charge then melts, as it is termed, "thick," and protects the banks from being cut. If too much silicon be present, however, and an excessive quantity of slag be formed, it will be found to be rather infusible, and unless care be taken to add the oxides quickly and follow the furnace up-thus rendering the slag more fusible by the extra iron oxide-the furnace bottom is liable to be pulled up. In such cases the author has frequently been able to warn

Nov 1, 1906

By William E. Ford, Edward Salisbury Dana

The monoclinic Wolframite Group and the tetragonal Scheelite Group are included here. Wolframite Group WoIframite (Fe,Mn)W04 a : b : c = 0.8300 : 1 : 0.8678 B = 89' 22' Hiibnerite MnW04 048362 : 1 : 0.8668 89' 73' WOLFRAMITE. Monoclinic. Axes a : b : c = 0.8300 : 1 : 0.8678; B = 89' 22'. mm"', 110 A 1TO = 79" 23'. ay', 100 A 101 = 62' 54' at, 100 A 102 = 61" 54'. $', 011 A 011 = 81" 54'. Twins: (1) tw. axis c with a (100) as comp.-face; (2) tw. pl. k (023), Fig. 449, p. 171. Crystals commonly tabular (1 a (100); also prismatic. Faces in prismatic zone vertically striated. Often bladed, lamellar, coarse divergent columnar, granular. Cleavage: b (010) very perfect; also parting (1 a (100), and 11 t (102). Fract,ure uneven. Brittle. H. = 5-5.5. G. = 7.2-7.5. Luster submetallic. Color dark

Jan 1, 1922

By J. E. Flinn, S. A. Duran

The steady-state creep behavior of poly crystalline cad mi inn was studied over a temperature range of (1.56 to 0.94 Tm. Two distinct mechanisms were found to occur over this temperature range. They were described by: where and represerqt the minimum strain rates corresponding to the low- and high-temperature regions, respectirely. The two regions of constant acti11ation energy were connected by a transition region where the strain rate was controlled by both mechanisms acting in parallel. At temperatures below a transition temperature of about 0.7 Tm the agreement between the activation energy value for creep and that for self-diffiision suggests a rate-controlling mechanism of dislocation climb. For cadwzium, steady-state creep at temperatures above 0. 7 Tm appears to be controlled by another mechanism, perhaps involving the behavior of dislocation jogs. FRENKEL et al.1 studied the high-temperature creep of polycrystalline cadmium and reported an activation energy of 21 kcal per mole for the 0.5 Tm < T < 0.8 Tm range. Based on observations of creep rate at only two temperatures, a value of 22.1 kcal per mole was determined by Medbury. These two investigations were for the purpose of showing agreement between the activation energy for creep and that for self-diffusion, reported3 as 18.2 and 19.1 kcal per mole, respectively, for diffusion parallel and perpendicular to the hexagonal axis. Gilman4 investigated prismatic glide in single crystals of cadmium over a higher-temperature range of 0.72 to 0.93 Tm, and found an activation energy of 29 kcal per mole. He also reported5 an activation energy higher than that of self-diffusion for prismatic glide in zinc single crystals deformed at temperatures near the melting point. This value was in good agreement with those found for an equivalent temperature range by Flinn and Munson6 and by Tegart and sherby7 for polycrystalline zinc. These two independent studies also disclosed at lower temperatures another value of activation energy near that for self-diffusion. It would be expected from the creep results on zinc and single-crystal cadmium that creep studies on polycrystalline cadmium, extended to temperatures near the melting point, might yield an activation-energy value higher than the 22 kcal per mole value found in earlier studies. The purpose of this paper is to report the steady-creep behavior of polycrystalline cadmium over a temperature range of approximately 0.5 to 0.9 Tm EXPERIMENTAL METHOD The cadmium used in this study was obtained in the form of as-cast rods, 0.5 in. diam, through the courtesy of the Bunker Hill Mining Co. The material was of 99.995 pct purity, as determined by spectro-chemical analysis. The creep specimens, which were 0.250 in. diam by 0.400 in. long and annealed at 300°C for 45 min to produce a stable average grain diameter 0.25 mm, were tested in compression using an apparatus similar to that described by Sherby.8 The specimen temperature was controlled to within ±0.5°C with the help of appropriate constant-temperature baths. The applied stress was maintained within 1.0 pct of the desired value by the additions of lead shot at fixed strain increments. No barreling was observed over the strains encountered during testing. Isothermal creep tests9 were used in the study with only a few differential temperature tests10 run for comparison purposes. Steady-state creep data were obtained over a temperature range of 60 to 287°C (0.56 to 0.94 Tm) at five stress levels ranging from 28.1 to 140.6 kg per sq cm. RESULTS The minimum or steady-state creep rate may be described by an equation of the following form:" where i is the minimum strain rate, S is the structure factor, F is a stress function, Qc is the energy of activation, T is the absolute temperature, and R is the gas constant. The minimum strain rates obtained in this study for cadmium were recorded on a semilogarithm plot as a function of the reciprocal absolute temperatures for the various stress levels, as shown in Fig. 1. This figure shows a characteristic transitional behavior" with a parallel interaction of two mechanisms. It is obvious that the activation energies corresponding to the individual processes are insensitive to stress because the curves are parallel. The discrete activation-energies values for the low- and high-temperature regions for the various stress levels are reported in Table I, and were determined by the least-mean-square method. For the low-temperature region, an activation energy of 20.7 ± 0.6 kcal per mole was obtained, and for the

Jan 1, 1967

By S. A. Lever, R. Hultgren

The solidus is usually the least satisfactorily determined portion of a phase diagram. Cooling curves, which succeed well with the liquidus, show the solidus inaccurately or not at all because of segregation which occurs during freezing. Heating curves of carefully homogenized alloys might be expected to indicate accurately the solidus, but they are seldom used. Dynamic methods involving heating or cooling are never completely satisfactory because of uncertainty as to whether equilibrium is attained. A static method in which the specimen may be allowed hours, days, or even weeks to attain equilibrium is to be preferred. In a static method a solid solution, for example, is first made thoroughly homogeneous, then heated to successively higher temperatures. After sufficient time at each temperature to assure equilibrium, some property is measured which should alter strikingly when melting begins. Microscopic examination can be used to detect the beginning of melting, but the method is tedious since the specimen must be quenched, sectioned, polished, and etched before each examination. Of all the physical properties which change on melting, electrical resistance is probably the most satisfactory to measure. The measurement may be made while the specimen is at temperature without damage to the specimen. It may be repeated indefinitely to ascertain when equilibrium has been achieved. Measurements may be made on a single specimen over the whole range of temperature. Most metals approximately double their resistance on melting. Since an accuracy of a few tenths of a percent is easy to achieve, the method is highly sensitive to the beginning of melting. In spite of these advantages, which have been perceived for a long time,l,2 a reasonable search of the literature has failed to reveal a single case in which the method has been satisfactorily applied in practice to the determination of solidus temperatures. The use of electrical resistance measurements appears to have been confined in practice to changes in the solid state. In the work described in the following pages we have applied the electrical resistance method to the solidus of the lead-tin system. We have found the method to be convenient, reproducible, and highly sensitive. We chose the lead-tin system because it leads to few technical difficulties. Furthermore, a number of determinations of solidus have been made in this system by various methods and results could be checked against them. However, all published results are not in good agreement with one another, so this work should help in determining the solidus more precisely. The Lead-tin Diagram Because of its commercial importance, there have been numerous investigations of the lead-tin diagram. The results of the most recent work on the solidus are indicated in Fig 7, as well as the results of the present work. The works of Honda and Abe3 and of Stockdale4 agree fairly well with each other and with the present work. Jeffery&apos;s5 data indicate the solidus to be about 50°C lower. Honda and Abe3 used differential thermal analysis on both heating and cooling cycles. Stockdale4 used the microscopic method and also differential heating curves. Stockdale&apos;s results were about 4" higher than those of Honda and Abe at low tin contents and lower at higher tin contents. These results also agree with those of Rosen-hain and Tucker.= Jeffery5 used electrical resistance measurements of the alloy as it was being heated or cooled. Apparently he did not attain equilibrium as his results are about 40°C lower than those of Stockdale4 or Honda and Abe.3 MATERIALS AND METHODS The lead and tin used were of high purity. They were supplied by the American Smelting and Refining Co., who gave the following analyses: Lead: silver, 0.0016 oz per ton; copper, 0.0008 pct; cadmium, 0.0007 pct; zinc, 0.0002 pct; arsenic, 0.0003 pct; antimony, 0.0002 pct; bismuth, 0.0005 pct; tin, 0.0001 pct; iron, 0.0020 pct; lead (by difference), 99.995 pct. Tin: antimony, 0.037 pct; arsenic, 0.020 pct; bismuth, 0.004 pct; cadmium, trace; copper, 0.025 pct; iron, 0.004 pct; lead, 0.020 pct; nickel and cobalt, 0.005 pct; silver, 0.0005 pct; sulphur, 0.005 pct; tin (by .-difference). 99.88 pct. One hundred grams of metal with the desired proportions of lead and tin was weighed out to the nearest one-tenth of a milligram. The mixture was placed in a silica crucible, covered with charcoal, and melted in a reducing atmosphere in a gas-fired furnace. The alloy was well stirred. Chemical analysis of two of the alloys checked closely with the weighed portions. The compositions of the remainder of the alloys were taken directly from the weighings, without chemical analysis.

Jan 1, 1950

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

WILLIAM B. PRICE* and PHILIP DAVIDSON, ? Waterbury, Conn. (written discussion?).-A few months ago we became interested in deter-mining the properties of. pure nickel as a metal for certain uses and arranged, in cooperation with the International Nickel Co., a series of tests on cold-rolled so-called pure nickel and both longitudinal and transverse specimens annealed at 100° intervals from 250° to 1050° C. Since our tests confirmed; in a general way, the observation put forth by Messrs. Browne and Thompson, they are given at this time. A bar of hot-rolled nickel about 9 in. (23 cm.) wide and 1/2 in. (12.7 mm.) thick made by the International Nickel Co. -of grade A stock, analyzing nickel plus cobalt 98.48 per cent., iron 0.67 per cent., manganese 0.27 per cent., carbon 0.07 per cent., silicon 0.162 per cent., sulfur 0.033 per cent., and copper 0.22 per cent., was cold-rolled down to a final thickness of 0.134 in., malting a 73.2 per cent. reduction by rolling. Test specimens, 9 by 1 in., cut parallel (marked longitudinal) and normal (marked transverse) to the direction of rolling were milled to give a test section 2 5/8 in. long by 0.5 in. wide. Three specimens each, longitudinal and transverse, were annealed at one time in a nichrome-ribbon-wound tube furnace. The temperatures were taken with a Pt-PtRh thermo-couple in conjunction with an Engelhard millivoltmeter. An annealing period of .) 2 hr. plus 25 min. preheating was used in all cases. Sclero-scopic and Brinell hardness tests and static tensile tests were made on the rolled and annealed specimens. The tensile tests are shown in graphic form in Fig. 7. The Brinell and scleroscopic values are given herewith.

Jan 11, 1919

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski&apos;s method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6&apos;7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6&apos;7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann&apos; suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in &apos;K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1&apos; values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

The world&apos;s production of petroleum in 1926 amounted to nearly 150 million long tons, of which India contributed 0.72 per cent. In 1927, this figure jumped to some 172 million long tons, of which the Indian proportion, on a practically stationary production, fell to 0.64 per cent. In 1928, there was another substantial rise in the world&apos;s production, which reached the figure of over 181 million tons. In 1929, there was another jump to over 202 million tons, but in 1930 the world&apos;s production fell to about 193% million tons, in 1931 to about 187 million tons, and in 1932 to about 183 million tons, while in 1933 the production rose again to about 202 million tons, in 1934 to about 215 million tons, and in 1935 to 233 million tons1. Decreases were shown by Poland, Sarawak, Egypt, Rumania and France. All other important producers showed an increase in production, by far the largest being due to Iraq, as a result of the opening of the pipe line to the Mediterranean. The United States contributed 60.9 per cent of the world&apos;s supply in 1935, Russia 10.7 per cent, Venezuela 9.4 per cent, Rumania 3.9 per cent and Iran 3.1 per cent. In 1928, India contributed 0.64 per cent, which fell to 0.60 per cent in 1929 and rose to 0.62 per cent in 1930, 0.63 per cent in 1931, and 0.64 per cent in 1932, and fell again to 0.62 per cent in 1933, to 0.60 per cent in 1934 and to 0.50 per cent in 1935; her position on the list of petroleum-producing countries fell from eleventh in 1929 to twelfth in 1930 to 1933, her place being taken by Trinidad and to thirteenth in 1934 and 1935, owing to the production by Iraq. The production of petroleum in India (including Burma2) increased slightly from 322,025,280 gal.3 in 1934 to 322,662,336 gal. in 1935, the highest figure in the history of the industry. The increase in 1935 is due to an increase of some 4 million gallons in Assam, almost offset by a decrease of 31/2 million gallons in Burma. This increase in output in 1935 was accompanied by an increase in estimated value amounting to Rs. 22,73,550 (£170,944).

Jan 1, 1937

By R. M. Brick

EDUCATIONAL benefits for veterans of World War II have largely removed one of the two former barriers to a college education for everyone, namely financial means and intellectual capacity. This latter limita¬tion has not kept privately endowed institutions from increasing 50 to 100 percent in size of student body, even after applying moderately rigid entrance standards. Growth of some land-grant universities, which cannot well exercise such restrictive judgements, has been even greater. After a weary board of admissions, subject to student, alumni, faculty, and even political pressures, has admitted double the former number of freshmen, the university&apos;s worries really begin: to find laboratory, classroom, and instructional facilities. If this were a one- or two-year problem, the answer would be simple: double up, hold night classes, particularly of laboratories, rent space, and have instructors work 24 class or contact hours a week instead of twelve (it takes usually two to three hours of outside work by the instructor for one hour in class). However, most engineering school faculty men are worn out now from four to five years of "accelerated" (frequently downward!) programs and they couldn&apos;t continue teaching in a way satisfactory to their own consciences on

Jan 1, 1947

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain&apos; and magnesia.&apos; Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann&apos;" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Nelson B. Russell, Donald C. Bond

The effects of various antifreeze agents on the formation of hydrogen sulphide hydrate have been studied. On a molar basis the relative lowering of Tm (the maximum temperature at which solid hydrogen sulphide hydrate can exist in equilibrium with the given solution) for the various agents is: sodium chloride 1.00, calcium chloride 1.71, methyl alcohol 0.57, ethyl alcohol 0.68, ethylene glycol 0.73, diethylene glycol 0.73, sucrose 0.87, dextrose 0.71. On a weight basis the relative lowering of TM is: sodium chloride 1.00, calcium chloride 0.91, methyl alcohol 1.08, ethyl alcohol 0.89, ethylene glycol 0.69, diethylene glycol 0.41, dextrose 0.23, and sucrose 0.15. Introduction The solid hydrate of hydrogen sulphide, H2S.6H20,1 is in equilibrium with water and liquid hydrogen sulphide at 85°F at a partial pressure of hydrogen sulphide approximately equal to the vapor pressure Of hydrogen sulphide at that temperature. At temperatures below 85°F, in the presence Of excess hydrogen sulphide (greater than the amount required to react with the water present) the hydrate is in equilibrium with liquid hydrogen sulphide at approximately the vapor pressure Of hydrogen sulphide. In the presence of excess water, the solid hydrate is in equilibrium with liquid water, containing dissolved hydrogen sulphide, at a pressure lower than the vapor pressure of liquid hydrogen sulphide at the same temperat~re.2 The lower the temperature, the greater the difference between the decomposition pressure of the hydrate and the vapor pressure of liquid hydrogen sulphide at that temperature. Conditions conducive to the formation of solid hydrogen sulphide hydrate may exist in wells producing a gas containing a high percentage of hydrogen sulphide under high pressure, or in the lead lines from such wells. This paper gives the results of tests made with various antifreeze agents which might be useful in decomposing the hydrate or in preventing the formation of the hydrate of hydrogen sulphide Apparatus Fig , shows a diagram of the apparatus used. The sample under observation was contained in a glass tube 34 cm long, having a 6 mm id and a wall thickness of 2.5 mm. The lower end of this tube was closed- with a plug of butyl rubber. The upper end of the tube was connected to a diaphragm gauge, with a stainless steel diaphragm, a manometer, a vacuum pump, and a cylinder of hydrogen sulphide, The tube was held nearly horizontal, with the liquid resting along the lower side of the tube. It was found that when the tube was held in a vertical position, it broke with ex. plosive violence as soon as it became filled with solid hydrate. Presumably this was caused by the expansion which occurred on solidification of the hydrate. The difficulty disappeared when the tube was held in an inclined position during the tests.

Jan 1, 1949

By R. Buehl

ALTHOUGH the main features of the transformations occurring in 18-8 have been published already,1-4 certain conclusions merit questioning and discussion. The questions may be summarized as follows: PERCENT REDUCTION BY COLD ROLLING FIG. 1.-VARIATION OF FERRITIC INDUCTION AND PERCENTAGE OF FERRITE WITH COLD REDUCTION. Composition of Alloy: C, 0.08; Mn, 0.40; Si, 0.24; P, 0.014; Cr, 18.13; Ni, 8.94. 1. If ferrite is formed by cold-working austenite, what happens to the carbon with which the ferrite and austenite are both pre-sumably supersaturated? 2. What is the nature of the alpha-ferrite formed at grain boundaries by chromium-carbide precipitation at these boundaries?

Jan 1, 1939

By Michael Hoch, Michel Desjardins

The isothermal section of the Mo-Ti-Zr-0 system at 1500°C was investigated using X- ray diffraction and mefallographic techniques. Up to 66.7 at. pct 0, the system contains ten four -phase regions. Isopleths at 10, 30, 45, 55, and 60 at. pct 0 were constructed. THE purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of molybdenum, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct o. PREVIOUS INVESTIGATIONS The Ti-Zr-0 system was investigated in this laboratory.&apos; The binary systems of interest have been compiled and discussed by Hansen&apos; and Levin, McMurdie, and Hall.3 Farrar, Stone, and Margolin studied the titanium-rich corner of the Ti-Mo-0 ternary. MATERIALS The titanium powder, 99.6 pct pure, the zirconium dioxide, and the molybdenum powder were supplied by the Fairmont Chemical Co. The zirconium powder,

Jan 1, 1962

By A. S. Nowick, E. S. Machlin

ONE of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.1 During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time required for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error.2~3 This method of showing stress-rupture data has been adopted by many investigators and the KACA.4 By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, 100, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time for rupture on stress, temperature, com- position, and structure. In order to obtain this information, an investigation was made at the KACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given com- position and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efficiency and power output of gas turbines used in aircraft propulsion can be increased. THEORY The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 eveloped by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate- process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process.&apos;&apos; For example, in a chemical reaction the unit process is

Jan 1, 1947

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m&apos;&apos;ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

ON Oct. 5, 1926, the day before the general ses-sions of the fall meeting of the American Insti-tute of Mining and Metallurgical Engineers at Pittsburgh, a round table conference on the combus-tibility and testing of coke was held at the Bureau of Mines Experiment Station. There were about fifty present, with A. C. Fieldner, chief chemist of the Bureau of Mines, as chairman. The following organi-zations were represented: American Institute of Min-ing and Metallurgical Engineers, American Society for Testing Materials, American Gas Association, Eastern States Blast Furnace and Coke Oven Association, Gas and Fuel Division of, American Chemical Society, and Southern Ohio Pig Iron and Coke Association. In opening the proceedings, Mr. Fieldner explained that the meeting had been called at the suggestion of several members of the Institute and members of other organizations. The subject is of interest to the pro-ducer and the user of coke whether it be in a blast furnace, cupola furnace, house-heating furnace, open grate, gas producer, or in a water-gas generator. There has been much confusion on this subject largely because there is no common definition of combustibility. Does the blast-furnace superintendent, the coke-oven operator, and the fuel engineer have the same under-standing of the term "combustibility"? If a common understanding can be reached, many differences of opinion will disappear. COMBUSTIBILITY OF COKE R. H. Sweetser of Columbus, Ohio, disagreed with the statement of P. H. Royster, T. L. Joseph, and S. P. Kinney in Reports of Investigations, Serial No. 2524, of the Bureau of Mines, in which it was stated that the coke-oven op-erator cannot change coke combustibility by modifying oven practice. Mr. Sweetser held that the coke-oven man can change the combustibility of coke. Blast-furnace men know that coke that will burn easily with low pressure and will. come down in the regular way in the furnace can be pro-duced from a given mixture of coal. His idea of the combustibility of coke is the rate of flow through the com-bustion zone of the blast furnace. If the coke does not pass through in normal manner it is highly incombustible. H. J. Rose of the Koppers Co., Pittsburgh, objected to being pinned down so closely on this phase of the com-bustibility and incombustibility of coke. Coke-oven men are frequently obliged to change oven conditions to make a coke which gives blast-furnace men what they want. The size of the coke and the screening have an important bear-ing on combustibility, and there are many cases on record where by simply changing the different sizes of the coke, everything worked smoothly, and that is a much more combustible coke.

Jan 1, 1927

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation&apos; dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,&apos; and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.&apos; A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954