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By K. R. Garr, D. Kramer, A. G. Pard

EXPOSURE of steels to a fast-neutron flux results in helium generation by (n,a) reactions. The elements Fe, Ni, Cr, and N are major participants in the (n,a) reaction and helium concentrations of up to 5 x 10"5 atom fraction could accrue in fuel clads after a year of service in proposed fast reactors.' Such concentrations of helium can severely reduce the ductility of alloys at temperatures of reactor service. The phenomenon of helium embrittlement has been studied in austenitic alloys which were irradiated with particles as a rapid means of producing significant helium concentrations.2-5 The pres-ent work is a continuation of those studies and is concerned with helium effects in a ferritic stainless steel. I) EXPERIMENT Small sheet tensile samples with a gage length of 0.50 in. and a cross-section of 0.009 by 0.040 in. in the gage length were punched from cold-rolled type 405 stainless steel. The composition of the steel used in this work is given in Table I. Prior to helium injection, the samples were annealed 24 hr at 760°C which caused complete recrys-tallization with a resulting grain size of 40 u. This treatment rendered the alloy completely ferritic and carbide particles, 0.5 to 2 uin size, were present at a density of 1 x 1011 cm-3, Fig. 1. These carbide particles were probably a mixture of the M7C3 and M4C types.6 Helium was injected into the samples by irradiation with a particles from a cyclotron, which produced uniform concentrations through the center two-thirds of the sample thickness. Details of this procedure were previously described.' The average helium concentration, as measured on a gas-source mass spec- 11) RESULTS A) Tensile Tests. The results of the tensile tests are given in Table I1 where the values shown are averages of two samples. There was no significant effect of helium on either the yield strength or tensile strength at 550" or 650°C but an increase in both is apparent at 750°C. Samples with helium showed a 20 pct loss in total elongation at 650°C which increased to a 55 pct loss at 750°C. The uniform elongation is not affected by helium at 550" or 650°C but shows an increase at 750°C.

Jan 1, 1970

By B. Silliman

THESE ores occur in the Laurentian rocks in the town of Clifton, St. Lawrence County, New York. The Clifton Mining Company have opened these magnetites upon their estate of 23,000 acres, on the waters of the Grasse River, an affluent of the St. Lawrence, which flows for about nine miles across the estate, exposing a section of the formation, and affording ample water-power at numerous points. In approaching this district from De Kalb Junction, upon the Watertown and Ogdensburg Railway, the observer passes from the zone of the specular ores, which abound to a great extent in Jefferson County, across a belt of non-metal-liferous limestones, continuing for some miles intermingled with metamorphic rocks, and gradually giving place to heavy beds of granitic and porphyritic gneiss, the weathered surfaces of which present a gray and rough appearance, from the washing out of the feldspar; leaving the quartz very prominent, and completely disguising the real character of the rock, which, when freshly broken, has a lively reddish appearance from the predominance of flesh-colored and red feldspar. Beds of fine-grained quartzite appear also intercalated in the granitic gneiss. These are the dominating rocks of the magnetite region, but the magnetite is always found, so far as the speaker's observation extended, associated with beds of calcite, carrying hornblende, black and green, biotite, and brown garnet interspersed with yellow and magnetic pyrites. The strike of these rocks is about northeast, and their dip about 40° to 45° southeast.

Jan 1, 1873

By G. C. Broadhead

THE lead district of Southeast Missouri covers an area of over 3000 square miles, including Maries County on the west, Jefferson on the east, Franklin on the north, and part of Madison on the south, or parts of ten counties. A general section of the rocks of the southeast part of this region would be about as follows, numbering from the top 1. Sandstone (the second of Missouri geologists), - 20 feet. 2. Cbert beds-beds of passage below, - 125 feet 3. Magnesian limestone, chert, and quartzite, - 100 to 300 feet 4. Lower magnesian limestone, - 100 to 150 feet 5. Gritstone and lingula beds, - 50 feet 6. Ozark marble beds, - 5 to 20 feet 7. Sandstone and conglomerate, - 5 to 90 feet 8. Porphyry, Archaean. 9. Granite, The thickness is approximate, for it is not possible to obtain the correct thickness of the various beds. No. 1 may be seen as de¬tached outliers or loose masses of a hard sandstone or quartzite, and is found on the hilltops in the southern part of Madison County, in like topographical position in Reynolds County and the western part of Washington County. No. 2 consists of alternations of chert, clay, and quartzite. It is the formation which contains most of the limonite deposits of Central and Southern Missouri. In Reynolds County shafts have pene¬trated it 75 feet. Outcrops there and in Madison would indicate it to be at least 125 feet thick. Fossils obtained in various places prove it clearly to be of the age of the calciferous sandrock of the New York system, and Nos. 1 and 2 may also be referred to the age of the second sandstone of Missouri. No. 3 consists chiefly of thick beds of ash, drab and flesh-colored magnesian limestone, both coarse and fine-grained. These beds, where they occur, in Washington, Jefferson, and the southern part of Madison Counties, contain a good deal of quartz in drusy cavities. In Washington County the limestones are beautifully ramified by a system of connected drusy cavities generally lined with minute quartz crystals arranged in botryoidal and mammillary forms, and called u mineral blossom " by the miners. This is the lead-bearing rock of Washington County, but in the southern part of Madison it does not appear to be galeniferous. It is also undoubtedly the equivalent of

Jan 1, 1877

By I. J. Gardescu

The production of petroleum in Rumania in 1932 totaled 52,560,000 bbl., an increase of 6.8 per cent over 1931. The average daily production rose from 123,000 bbl. at the beginning of the year to 173,000 bbl. at the end of the year, the production in the Gura-Ocnitzei field rising from 38,800 to 80,700 bbl. per day. This increase was due to competitive development during which time the percentage of total production of the various operating companies remained practically unchanged. Chief producers were: Concordia, 30.3 per cent; Unirea, 21.6; Romano-Americana, 13.5; Steaua Romana, 8.3. Boldesti, where production of the previous year was practically doubled, would have produced far greater quantities were it not for the fact that both Astra Romana and Romano-Americana curtailed drilling operations. Of the total daily production of 21,800 bbl. a day, the Astra Romana, Steaua Romana and Romana Americana, produced respectively 67, 25 and 8 per cent. The Moreni field showed a sudden drop in production from the preceding year, due primarily to reduced drilling activities. Its production of only 21,000 bbl. a day removes it from first position for the first time in many years. All the other fields showed a decrease in production, except Ochiuri, 3 miles west of Gura-Ocnitzei, and Ceptura, 12 miles east of Boldesti. Drilling1 During the first nine months of 1932, 116 wells were completed, 8 of which were dry holes. The Meotian (lower Pliocene) is the producing horizon in 73, the Dacian (upper Pliocene) in 31, and the Oligocene in 4 of the completed wells. Three of the Oligocene wells were drilled in the Bacau district and one at Grausor, near Campina. In addition, 47 wells were drilling on Oct. 1,1932. Of the total completions and drilling wells, 92 per cent employed rotary for a footage of 98.5 per cent of the total drilled. Power for rotary drilling was furnished to 105 wells by steam, to 38 by electricity, and to one by gasoline.

Jan 1, 1933

Iron Ore Resources of the World (Die Eisenersvorrate der Welt)_ By G. Einicke. Verlag Stahleisen, Dusseldorf, 1950. 418 p., with 192 tables and an atlas volume containing 100 p. of reaps. 66 German Marks.-A notable work in which the latest available information on iron ore deposits has been compiled by diligent work, continent by continent, country by country. The author reveals the effect of geological formations, iron content of ore, accessability, cost of transportation, political and economic considerations. Ore beds of importance to the German iron and steel industry are given more space than others. The bibliography contains almost 250 references. A tragic comic feature is the author's complaint that as soon as a map of iron ore resources of a country has been completed, the country's boundaries are changed. Reviewed by W. Trinks, Carnegie Institute of Technology. Industrial Research Laboratories of the United States. National Research Council, Washington, D. C. Ninth Edition. 1950. 445 p. $5.-Contains information on the research laboratories of 2845 industrial and commercial organizations, including names of research executives, location of labs, types of activity, whether any consulting services are offered. There are two appendices, one of which lists data on government labo ratories which cooperate with industry, and the :)ibex naming universities and colleges offering research services to industry.

Jan 2, 1951

By B. Silliman

THESE ores occur in the Laurentian rocks in the town of Clifton, St. Lawrence County, New York. The Clifton Mining Company have opened these magnetites upon their estate of 23,000 acres, on the waters of the Grasse River, an affluent of the St. Lawrence, which flows for about nine milt",3 across the estate, exposing a section of the formation, and affording ample water-power at numerous points. In approaching this district from De Kalb Junction, upon the Watertown and Ogdensburg Railway, the observer passes from the zone of the specular ores, which abound to a great extent in Jefferson County, across a belt of non-metal-liferous limestones, continuing for some miles intermingled with metamorphic rocks, and gradually giving place to heavy beds of granitic and porphyritic gneiss, the weathered surfaces of which present a gray and rough appearance, from the washing out of the feldspar; leaving the quartz very prominent, and completely disguising the real character of the rock, which, when freshly broken, has a lively reddish appearance from the predominance of flesh-colored and red feldspar. Beds of fine-grained quartzite appear also intercalated in the granitic gneiss. These are the dominating rocks of the magnetite region, but the magnetite is always found, so far as the speaker's observation extended, associated with beds of calcite, carrying hornblende, black and green, biotite, and brown garnet interspersed with yellow and magnetic pyrites. The strike of these rocks is about northeast, and their dip about 40' to 45' southeast

By H. A. Schwartz, W. Kenneth Bock

IN this paper it is shown that when the tensile strength of a given steel in various states of heat-treatment is plotted against its elongation, a straight line results. The equation of this straight line can be computed with considerable accuracy from its chemical composition. The appropriate equations are given. The logarithm of the slope of the tensile-strength locus is shown to be proportional to the cumulative effect of the total alloy addition and the position of the line to be directly proportional to the cumulative effect of the alloy content. It is further pointed out that heat-treatment is more effective than composition in determining yield ratio. The latter enters mainly by its effect on hardenability, which is briefly discussed. Reduction of area and Brinell number are given some incidental attention. The data are applicable only to steels that have been normalized and/or quenched. The steels, if normalized, may or may not have been tempered. If quenched they must have been tempered at or above 400°C. (750°F.).

Jan 1, 1944

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By N. J. Grant, B. C. Giessen, U. Wolff

With the aid of the splat-cooling technique of rapid quenching, metastable alloy phases based on antimony ad bismuth have been prepared. At room temperature, simple cubic phases were found in the Sb + Au, 56 + Yd, and Sb + Ni systems. Another phase was retained in the Au-Bi system at -190°C; in this systent, a microcrystalline phase and a rhombohedrally distorted phase were also observed. The crystal chemistry of these phases is discussed in terms of their valence electron concentration range. A remarkable five-step Phase sequence was found upon heating and equilibration of certain metastable Au-Bi alloys. USING the splat- cooling technique of rapid quenching from the liquid,' a large number of metastable intermediate alloy phases have been prepared in recent years. Thus, Hume-Rothery phases of the hexagonal type based on the valence electron concentration have been produced in systems where they are missing in equilibrium, e.g., Ag-Ge 1 or AU-Sb. 3 In a comprehensive study of metastable alloys based on tin, simple hexagonal metastable y phases were found, raising the total of stable and metastable y phases from 3 to 13. 4 In the In-Bi system, five new metastable intermediate phases were retained.' In most cases, the new metastable phases have some crystal chemical characteristics in common: a) They have rather simple, elementlike structures with few atoms per unit cell, e.g., y phase,4'5 or the metastable primitive cubic phases in the Ag-Te and and Au-Te systems.= b) Their structures are often related to those of the terminal phases, or to elements that are straddled in their position in the periodic table by the constituent elements; this is the case for metastable ß (In-Bi) with the structure of white ß Sn,' or metastable a (Cd-sn). 4 c) They seem to represent the crystal structures appropriate to certain average group number (AGN) ranges in which no or few single-phase structures exist in equilibrium. These average group number ranges can probably be equated in the case of many elements of the Ba(Zn)-Bs(As) groups with the averaged valence electron concentration. In the present work, the splat-cooling technique has been applied to the alloys of antimony and bismuth. In equilibrium, neither element forms intermediate alloy phases with other B elements from groups Bl(Cu) to B4(Si) that contain more than 66.7 at. pct of Sb or Bi, respectively, e.g., AUSb 2. 7 Thus, antimony- or bismuth-rich phases, which might be closely related to antimony or bismuth, and which would reflect struc- tural changes occurring on alloying with small amounts of addition elements, do not exist. Also, the terminal solubility of antimony and bismuth for all B metals is very small. It was therefore of interest to investigate the influence of enforced, nonequilibrium solid solution of addition elements in antimony and bismuth on their crystal structures. It was found that additions of group B 2-B4 metals act distinctly differently than additions of group T 10 and B1 metals. The latter set of additives will be treated here. EXPERIMENTAL TECHNIQUES Alloy preparation and splat-quenching followed closely the procedures described in Refs. 1, 4, and 5; they consisted of the preparation of master alloys from high-purity starting materials (99.99+ pct) and blast-atomizing of 20-mg quantities onto copper sheets. The resulting approximately 1 to 5 u thick foils were investigated by X-ray diffraction. The cooling rates obtained are of the order of 107 to 10 8 C per set,'" causing solidification to proceed at a rat; of approximately 100 cm per sec.' Powder patterns of the resulting fine-crystalline materials were taken with filtered CuK, radiation. For antimony alloys the substrates were held at room temperature and for bismuth alloys at -190°C both during splat foil deposition and X-ray investigation. Annealing treatments at several

Jan 1, 1969

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

By Carl Beal

Introduction. DURING the latter part of 1915 and the first half of 1916, the writer held the position of geologist in connection with the conservation work instituted by the U. S. Bureau of Mines, on oil and gas land belonging to the Indians of the Five Civilized Tribes in Oklahoma. The duty of the geologist was to correlate formations containing oil, gas,-and water, and to determine the relations of these substances in the different formations so that the conservation agents might carry on their work most intelligently. On account of the rapid development of the Cushing field, which lies in the western part of the Creek Nation, much work was clone there by the inspection force. In the course of the geologic studies a large amount of information was collected, which, on analysis, has disclosed some interesting facts worthy of publication. The report, of which the following remarks are an abstract, has been prepared and submitted to the U. S. Geological Survey for publication. This report is now (June, 1917) in the press and will doubtless be issued in a few weeks. Methods Used In addition to the structure maps showing the folding of the Pawhuska limestone, which crops out in several places in the Coshing field, separate structure maps of the three most important productive sands-the Layton (Fig. 2), Wheeler, and Bartlesville-have been prepared. These structure maps, were prepared by obtaining the logs of nearly all the wells

Jan 8, 1917

By Carl H. Beal

DURING the latter part of 1915 and the first half of 1916, the writer held the position of geologist in connection with the conservation work instituted by the U. S. Bureau of Mines, on oil and gas land belonging to the Indians of the Five Civilized Tribes in Oklahoma. The duty of the geologist was to correlate formations containing oil, gas, and water, and to determine the relations of these substances in the different formations so that the conservation agents might carry on their work most intelligently. On account of the rapid development of the Cushing field, which lies in the western part of the Creek Nation, much work was done there by the inspection force. In the course of the geologic studies a large amount of information was collected, which, on analysis, has disclosed some interesting facts worthy of publication. The report, of which the following remarks are an abstract, has been prepared and submitted to the U. S. Geological Survey for publication. This report is now (June, 1917) in the press and will doubtless be issued in a few weeks. Methods Used In addition to the structure maps showing the folding of the Pawhuska limestone, which crops out in several places in the Cushing field, separate structure maps of the three most important productive sands—the Lay-ton (Fig. 2)) Wheeler, and Bartlesville—have been prepared. These structure maps were prepared by obtaining the logs of nearly all the wells

Jan 1, 1918

THE foundation established by the partners of the late Robert W. Hunt provides for both a medal and a prize. The latter has not been given before this year, and the first award is to C. H. Herty, Jr., for his several papers on the physical chemistry of the open-hearth process.. He is the son of the well known chemist of the same name. He was born at Athens, Ga., on Oct. G 1896, graduated from the University of North Carolina in 1918, and went into war service as foreman of U. S. Chemical Plant No. 4, at Saltsville, Va. In 1919 he went to Massachusetts Institute of Technology, where he was successively instructor, research assistant, and research associate in the School of Chemical En-gineering practice receiving his master's degree in 1921 and his Ph.D. in 1924. He continued his brilliant work on the physical chemistry of the open-hearth process, much of it being done in cooperation with the Bethlehem Steel Co. at its Lackawanna plant, and dealing with the elimination of sulfur. In 1926 he joined the staff of the U. S. Bureau of Mines, in charge of its ferrous metallur-gical work at Pittsburgh, and continues to be active in research work on the physical chemistry and metallurgy of the open-hearth process. His Institute publications are: Some Factors Affecting the Elimination of Sulfur in the Basic Open-hearth Process," "Chemical Equilibrium of Manganese, Carbon and Phosphorus in the Basic Open-hearth Process" and "Desulfurizing Action of Manganese and Iron," and he will present a paper on ?Effect of Temperature on the Solubility of Iron Oxide in Iron" at the annual meeting.

Jan 2, 1928

By AIME AIME

THE meeting" of the Rare Minerals and Metals Committee was held Monday afternoon, Feb. 17; Donald M. Lidclell, chairman, presiding. The first paper (T. P. 279), "Progress in the Use of Tantalum," by George W. Sears, was read by Mr. Smyth. Dr. Sears' paper contains an interesting summary of the uses, alloys and ores of tantalum and a resume of present method of reduction. The uses of tantalum is based on its extreme rise to the reaction of even the strong mineral acids, its great avidity for the common gases and its capacity for transforming alternating to direct current. Tantalum, as an alloy material, has received considerable study and many alloys have been reported. Among them three types appear to .be most prominent, alloys of high melting point, hard alloys and acid rising alloys. As the estimated quantity of tantalum in the earth's crust is less than that of gold, it must be looked upon as n rare metal. Australia is the greatest producer and the Black Hills of South Dakota produce minor amounts. As the one type of mineral available contains both tantalum and columbium, the extracting and metallurgy of tantalum are difficult chemical processes. Greater simplicity in this and the development of a market for columbium would undoubtedly be of great benefit to the tantalum industry, andl make for a greater use of tantalum produced.

Jan 1, 1930

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' 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,' 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.' 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

By R. N. Hoffman

A new technique for determining capillary pressure curves has been developed and tested. The technique differs from previously reported centrifuge techniques in that the centrifuge is slowly accelerated from zero to the maximum desired speed rather than being held constant at particular, progressively higher speeds. An important advantage of this technique over other methods of determining capillary pressure curves is the short time required to obtain the desired amount of data over the chosen pressure range. For example, to obtain 30 data points between 1.2 and 104 psig with a 1.55-in. long, 3/4-in. diameter core using a brine-air system, 6.6 hours were required with this technique. An equally important development of this paper is an analytic method for the conversion of the data from the centrifuge experiment to capillary pressure curve data. Previously there has been only an approximate conversion available. Although the capillary pressure curves determined by this technique appear to be as accurate as those determined by other techniques, the accuracy could be improved if certain variables, not treated in this experiment, were investigated. Among these are the dynamic distortion of the centrifuge equipment and imperfect initial saturation of the cores. INTRODUCTION Pirson 1 defines capillary pressure in a porous medium as "the differential pressure that exists between two fluid phases at their interfaces when they are distributed under static equilibrium within a porous material". Capillary pressure in rocks is known to be a function of fluid saturation, among other things, and a capillary pressure curve is defined for the purposes of this paper as a plot of the capillary pressure-wetting phase saturation relationship for a particular rock sample. Several methods are used for determining capillary pressure curves for small rock cores. Prominent among these are the semi-permeable barrier, mercury injection, and, to a lesser extent, centrifuge methods. The semi-permeable barrier method is currently the most popular. It features simplicity in both execution and the mathematical conversion of the experimental data into a capillary pressure curve. The main disadvantages of the semi-permeable barrier method are the time required — as long as two months — to obtain several points for the curve, and a fairly low maximum pressure before breakthrough of the non-wetting phase into the barrier occurs, for example, about 32 psig for a brine-air system. It is for these reasons that other methods such as the centrifuge method have been introduced. High accelerations and the absence of a barrier result in quicker attainment of saturation equilibrium at a given pressure. However, the centrifuge method involves much more expensive equipment and more difficult procedures and calculations than does the barrier method. The purpose of this investigation has been to improve the equipment and procedures of the centrifuge method and to develop an analytic method for the conversion of the experimental data into a capillary pressure curve. Hassler and Brunner did the original work in the determination of capillary pressure using a centrifuge. In their work the centrifuge speed was increased in a step-wise manner, each speed being held constant until saturation equilibrium was reached in each core. Saturation equilibrium was indicated when the volume of liquid collected in the graduated pipette of the core holder remained constant. According to Hassler and Brunner, equilibrium was reached in "a few minutes to one-half hour or more". In the centrifuge method, as opposed to the barrier method, the fluid saturation of the core is not a constant throughout the length of the core, but varies with the radius of centrifugation. Also, the capillary pressure cannot be read directly but must be calculated from a knowledge of the centrifuge speed and other parameters. For these calculations, Hassler and Brunner derived the following equations:

By Irving Fatt, R. M. Weinbrandt

Efforts have been made for many years to observe pore structure of sedimentary rocks on a microscopic scale. A better description of the pore structure in reservoir rock would aid in the development of relations between flow through tube network models and flow in consolidated reservoir rock. The unique qualities of the scanning electron miscroscope (SEM) make it the ideal tool to use in a study of pore structure. Previous methods of studying pore structure included plastic casts of pore space and optical microscopy.l-7 There is now available a new method to observe three-dimensional flow channels in reservoir rock: a scanning electron microscope having variable magnification from X20 to X20,000 and approximately 1000 times the depth of focus of the conventional light microscopes. This microscope also can obtain stereoscopic images and can measure and diagram flow channels so that it is possible to construct a network of tubes that will model consolidated reservoir rock. THEORY OF THE SCANNING ELECTRON MICROSCOPE The scanning electron microscope (SEM) functions by projecting a beam of electrons through magnetic focusing lenses at a specimen and recording secondary electrons excited by the primary beam. The amount of secondary electron emission portrays the topography of the specimen because more secondary electrons are emitted from high points than from low points. A schematic of the SEM is shown in Fig. 1. The property of the SEM that is of most importance in this study is its great depth of focus. The depth of focus results from using electrons

Jan 1, 1970

By David N. French

In a recent paper, Miyoshi, Hara, and sugimotoL have shown that hardness increases and crack resistance decreases with polishing time in tungsten car-bide-cobalt alloys. They attribute the changes in hardness and crack resistance to cold working in these alloys. More recently Exner2 explains the decrease in crack resistance with the amount of material removed (polishing time) by suggesting that polishing removes a high compressive residual surface stress due to the initial grinding operation. He cites previous work on steel to show grinding can induce surface compressive stresses but offers no direct experimental measurements to support this in cemented tungsten carbides. In recent work we have observed changes in residual stress in the W C phase as measured by X-ray diffraction techniques with changes in polishing conditions.3 As a result of the work of Miyoshi et al.,L a brief study was undertaken to investigate the effects of polishing and grinding on the residual stress in the WC phase and have been reported.4 A single composition of tungsten carbide —10 wt pct Co was used. Two initial conditions were studied: an annealed condition with about -30,000 psi residual stress from the differences in thermal coefficients of expansion of WC and cobalt and, on the same specimen, a surface ground with a 150 grit diamond wheel. Stress was measured in the WC phase using X-ray diffractometry as a function of the amount of material removed by metallographic polishing with 6 diamond paste. The results are shown in Fig. 1. Two things are noted, 1) polishing with 6 p diamond paste has little effect on the annealed sample and 2) the magnitude of the grinding stress is markedly reduced as material is removed. By the time 0.1 mil is removed the surface has a metallographic polish satisfactory for light microscopy examination. Thus the surface, even though polished, can still retain most of the stress due to grinding. Since WC is itself slightly ductile, it seems reasonable that high compressive stresses can be generated in the surface by the plastic deformation accompanying grinding. Exner2 suggests, by analogy with steel, that as a result of grinding both WC and cobalt in the

Jan 1, 1970

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By Charles R. Keyes

PAGE. I Introduction,........674 11. Occurrence............ 676 III. Geology of Death Valley BoRate-Region,....677 1. Surface.Relief ......677 2. Geologic Formations,....680 3. Geotectonics,..684 IV. FURnace Canyon Deposits..686 1. General Features..686 2. Geologic Structure..688 3. Ores.....690 4. Typical Section ...691 V. Lost Valley Deposits...693 VI. Mojave Desert Deposits..693 1. Distribution....693 2. Geologic Structure ........694 3. Ores............ 696 VII. Santa Clara Valley Deposits .699 1. Distribution....699 2. Geologic Structure..700 3. Ores.....700 VIII. Ventura County Deposits..701 IX. Geologic Occurrence of Borax .701 1. Original Sources...701 2. Solfataric Borax...702 3. Lacustrine Borax...703 4. Marsh Borax....703 5. Terranal Borax...704 X. Chemistry of Natural Borates.... 705 1. General Considerations.....705 2. Composition of Saline Waters...706 3. Solubility of Components....707 4. Time-Element in Water.Concentrations . 707 5. Effect of Temperature.....708 6. Effect of Pressure......709 XI. Occurrence of Other Commercial Salines,.... 709 I. Introduction. A complete transforrnation has taken place in the borax industry during the year 1908. A most remarkable factor in

Jan 1, 1910