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By John C. Shyne, Eric R. Morgan

BORON as a hardenability agent of commercial importance has been the subject of extensive study in recent years. It has been suggested in the past that boron increases hardenability by combining with nitrogen, thus rendering it innocuous.&apos; More recently it has been proposed that boron increases hardenability by reducing the free energy of sites of ferrite and pearlite nucleation.&apos; The segregation of boron to grain boundaries, the primary site of nucleation, would account for the large hardenability effect of minute additions of boron in steel. This grain boundary theory has found general acceptance while the concept of boron as a nitrogen scavenger has been disregarded. However, the interaction of boron and nitrogen in steel is considered to be important to hardenability because boron may be made ineffective by combination with nitrogen.". * The present work was undertaken to examine some of the effects of boron and nitrogen arid their interaction in steel. A base composition of moderate hardenability was chosen. This was a 0.35 pct C steel containing 2.50 pct Ni and 0.30 Mo. This composition was used because it contained no strong carbide, nitride, or Table I. Composition of Steels by Analysis, Wt Pct Steel C Ni Mo 0&apos; B N* Base 0.35 2.50 0.30 0.0012 nil <0.0001 Boron 0.35 2.50 0.32 0.0012 0.0022 <0.0001 Nitrogen 0.33 2.60 0.35 0.0015 nll 0.0052 Boron plus nitrogen 0.35 2.48 0.30 0.0006 0.0020 0.0040 * Obtained by vacuum fusion technique. boride-forming elements. The other alloys examined were modifications of the base composition and contained nitrogen, boron, or nitrogen plus boron. The compositions of the four alloys used are listed in Table I. The alloys were vacuum melted from electrolytic iron, electrolytic nickel, ferromolybdenum, and fer-roboron. When required, nitrogen was added by admitting a partial pressure of nitrogen over the melt after vacuum melting. The alloys were cast into 21h-in. diam ingots and hot rolled to %-in. sq bars. No ingot pattern was discernible on the polished and etched cross sections of the hot-rolled bars. The alloys were normalized at 1650°F, then machined into standard %-in. diam end-quench hardenability test bars. Four different austenitizing treatments were used: 60 rnin at 1550°F, 45 rnin at 1800°F, 30 rnin at 2000°F, and 20 rnin at 2000°F followed immediately by 30 rnin at 1550°F. The 1550" and 2000°F treatments were carried out in duplicate for each of the four steels. In order to prevent surface oxidation the bars were austenitized while buried under charcoal in an atmosphere of argon. After quenching the bars in a conventional end-quench fixture, the hardness surveys were made in the usual fashion on parallel flats ground along opposite sides of each bar. These were ground 0.050 in. deep rather than the conventional 0.015 in., to avoid decarburized or deboronized regions.5 The austenite grain sizes which resulted from each heat treatment were observed metallographically using Vilella&apos;s etch for martensite. The criterion used as a measure of hardenability was the distance from the quenched ends of the bars at which a hardness of RC 35 was observed. This hardness represented the inflection point on the hardness vs distance plot. Fig. 1 shows the hardenability of each steel after the several heat treatments. The duplicate tests demonstrated excellent reproducibility; the distance to Rc 35 was reproduced within 1/16 in. for duplicate test bars. All four alloys had the same grain-coarsening characteristics. Neither boron nor nitrogen had any observable effect on grain size. The grain sizes resulting from the various austenitizing treatments were ASTM 7 at 1550°F, ASTM 4 at 1800°F, and ASTM 2 at 2000°F. The small amount of boron in the boron steel greatly enhanced hardenability when the samples were austenitized at 1550°F. The low hardenability of the boron plus nitrogen steel showed that nitrogen eliminated the boron contribution to hardenability. Both steels containing nitrogen, with and without boron, exhibited lower hardenability than the base composition when quenched from 1550°F.

Jan 1, 1958

By F. P. Haver, M. M. Wong

The Federal Bureau of Mines has developed a leach= electrolysis method for recovering lead from galena (PbS). Flotation concentrate is leached with ferric chloride (FeCl3) solution to obtain lead chloride (PbC12) and elemental sulfur, PbS + 2FeC13 -+ PbC12 + 2FeC12 + Sº. Over 99% of the P~S in the condentrate is converted to PbC12. The leach solution, composed of brine (NaC1) and FeC13, dissolves the PbC12 as it is formed, leaving a residue of elemental sulfur plus gangue. Very pure PbC12 (>99.9%).is crystallized from the leach filtrate on cool- ing and is subsequently electrolyzed in a fused-salt bath to obtain molten lead metal (>99.9% Pb). Spent leach solution (FeC12) is regenerated for further use by reaction with the chlorine obtained in the electrolysis of lead chloride, and other values, such as Ag, Cu, Zn, and Sº, are recovered by additional treatments of the leach solution and leach residue. This paper discusses results and conditions of the leaching and electrolysis operations.

Jan 1, 1976

By Hermann Schmalzried, Carl Wagner

UPON heating a metal oxide or sulfide in H2, first only oxygen or sulfur is removed from the surface. Thus the metal/nonmetal ratio in the oxide or sulfide increases and the thermodynamic activity of the metal increases accordingly. For the formation of metallic nuclei, a certain super saturation is necessary, i.e., the activity of the metal must become greater than unity. Once nuclei of the metal have been formed, the supersaturation is supposed to decrease. Even under steady-state conditions of a reduction process, however, the activity of the metal inside an oxide or sulfide phase must be greater than unity in order to have a driving force for the individual steps of the reduction process. As an example, consider the reduction of Ag2S with a high mobility of cations and electrons. As shown schematically in Fig. 1, the reduction process involves the following steps:&apos; 1) sulfur removal along the entire Ag2S surface in form of H2S, 2) migration of Ag&apos; ions and electrons from the Ag2S surface to nuclei of metallic silver, 3) transfer of Ag+ ions and electrons from the Ag2S phase to the metal. For a finite rate of step 3, the activity of silver in Ag2S next to the Ag2S-Ag interface must be greater than unity. Moreover, for a finite rate of step 2, the activity of silver at the gas-Ag2S interface must be still somewhat greater. Theoretical considerations lead to the tentative conclusion that at least under steady-state conditions the supersaturation will be rather low.&apos; To test this conclusion, the average activity aAg of silver in a Ag2S tablet about 2 mm thick with a diameter of 5 mm was followed as a function of time by measuring the electromotive force E of the cell Pt I Ag | Agl I Ag2S I Pt where AgI is used as a solid electrolyte in which only Ag+ ions are mobile. The activity aAg is calculated as aAg=exp(-EF/RT) Since the diffusion coefficient for transport of silver in Ag2S is very high (- 3 . l0-2 sq cm per sec),3 the average activity aAg is representative for both the bulk and the surface of the Ag2S tablet. Experiments were conducted at about 400°C. The cell was surrounded by an aluminum block in order to secure a uniform temperature and to eliminate thermoelectric effects. With the help of a potentiometer, first a potential of 0.16 v was applied to the above cell in argon in order to obtain a well defined initial state with a Ag/S ratio close to 2.000.~ Then the cell was disconnected from the potentiometer and a gentle stream of H2 was passed along the Ag2S surface. In view of the removal of sulfur in form of H2S, the electromotive force E decreased within 20 to 30 min to zero corresponding to a Ag/S ratio of 2.003 and became negative, indicating a value of aAg> 1. A representative plot electromotive force E vs time is shown in Fig. 2. The minimum of the electromotive force characteristic of the onset of

Jan 1, 1963

By H. E. Stauss, J. Hino

INTEREST in silicon has arisen again in the past decade as a result of improvements in crystal rectifiers.&apos; Although the preparation of silicon was first reported by Berzelius in 1880, the early product was of relatively low purity, and only the need for rectifiers in World War II led to the production of a 99.9+ pct pure powder. This material in crystalline form was consolidated into massive silicon for use, and the method developed was to melt it with selected added constituents as "doping" agents. Melting techniques, therefore, are of great importance. There are two basic problems in producing silicon ingots free of doping additions; one is the prevention of spitting and the other is prevention of cracking of the ingot during freezing. The most satisfactory arrangement yet developed for producing massive silicon is to melt and freeze in a cylindrical quartz crucible surrounded by a concentric heating element and concentric radiation shields or insulation. For example, use can be made of a tubular heater with a high frequency generator as the source of power and reflecting shields of alundum cylinders. The spitting of silicon is related to gas evolution, and the gas comes from two primary causes—adsorbed gas and the reaction products of silicon and the crucible. Gas is also released from bubbles contained in the quartz crucible walls. Improved removal of adsorbed gas can be achieved by means of controlled melting and freezing. The seriousness of the problem in vacuo is reduced with an electrically operated mechanical movement of the high frequency power coil. The upper portion of the powder charge is melted first and the high frequency coil lowered until the powder is completely molten. During cooling the high frequency coil is raised slowly. These means also reduce the final nonviolent extrusion of large beads of metal through the ingot top during freezing. Better control of spitting and bead extrusion is obtained when melting is done under helium at. atmospheric pressure instead of in vacuo. The problem of reaction between silicon charge and crucible in practice is confined to the reaction between silicon and quartz. This2 apparently is: Si + SiO2 + 2SiO The part that this reaction plays in spitting has not been isolated for separate study. SiO is a volatile vapor at the melting point; of silicon and is released freely during melting in vacuo, but hardly at all in helium at atmospheric pressure. The cracking of ingots is a major difficulty in melting silicon, and its prevention requires special melting techniques or the addition of "toughening" agents such as aluminum or beryllium.&apos; The cracking of the ingots has been explained as being the result of the expansion that occurs upon freezing; although direct observation of freezing ingots reveals visible cracks on the surface only after a red heat has been reached, suggesting that cracking is the result of differential contraction of silicon and quartz. Silicon wets quartz, and the ingot adheres tightly to the crucible. Therefore as ingot and crucible cool, the two either have to pull apart, or at least one must crack. Surprisingly, in spite of the relative thinness of the quartz and the thickness of the ingot, the ingot and the crucible both crack. Microscopic and X-ray4 studies fail to show any plastic flow other than twinning in the ingots. Slow cooling fails to prevent cracking. Another possible solution to cracking is to weaken the crucible. Use of thin-walled crucibles finally led to success with fused quartz crucibles with a wall thickness of 0.25 to 0.50 mm. With such thin-walled fused quartz crucibles consistently uniform success is secured in producing sound ingots 30 mm in diam from the purest available grade of silicon (99.9+) without the use of any type of addition. Melts are made in the size range of 50 to 100 g. Omission of a deliberately added doping agent is not sufficient to insure pure ingots. The reaction of silicon with crucibles and the resultant solution of impurities in the silicon is well-established." In this laboratory, the presence of Al, Be, and Zr has been found spectroscopically in ingots melted in contact with alumina, beryllia, and zircon. The best crucible materials reported in the literature are MgO and SiO2. Use of MgO in this laboratory has resulted in a heavy deposit of magnesium on the furnace walls, showing that a reduction of the magnesia occurred and the resulting magnesium removed from the melt by volatilization. In the case of quartz, the silica is reduced and SiO liberated to deposit on the equipment walls. There probably is real danger that oxygen is dissolved in the ingot when either magnesia or silica is used as the crucible material. Preliminary analyses by Dean Walter in his vacuum unit in this laboratory6 indicate the presence of oxygen in undoped silicon melted in quartz.

Jan 1, 1953

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull&apos;s suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin&apos;s observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin&apos;s studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several &apos; strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r&apos; phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

Report of the Americanization Society, New York Section During the past two months the Americanization Committee has held social meetings of various kinds for foreign-born women, as a preliminary to future effort along the lines of Americanization work. At the same time, a thorough investigation was made as to the work being done in New York by organizations devoted to this interest. The committee will be very glad to help any other committees being formed, in mining centers, with advice and information that has been gathered together as to classes and meetings of all kinds best suited to the needs of a foreign-born population. The work has been so extensively taken up in New York that for the present it would seem to be, for this committee, the most profitable and interesting work to continue the social meetings and to undertake the care of one or more immigrant families, to be friend and adviser in joy and sorrow, work and play, and in this way do some fundamental Americanization work. Respectfully submitted, LAURA G. BURGER, Chairman.

Jan 6, 1918

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson&apos; have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry&apos; estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

By Oswald J. Heinrich

SINCE my communication to the Institute at the Baltimore meeting in 1879,* in which I took the lead in emphasizing the importance of a new method in the manufacture of soda, already practiced to some extent in England and on the Continent of Europe, five years have passed. I.then referred particularly to the advantages offered in the United States for this peculiar method, by the ammonia process, namely: 1. At the present time, at least, we have but one mine in this country where rock-salt is mined, namely, at New Iberia, La. On the other hand, we have many localities where brine of various degrees of strength, up to that of cold saturation, is obtained in large quantities. 2. We have excellent fuel, in close proximity to most of the brinecenters. 3. Our supplies of pyrites, to use in the manufacture of sulphuric acid, for use in the manufacture of soda by the Leblanc process, are mostly too far from the brine-centers to permit competition in that line with the more favorable conditions existing in England. 4. Unlike our foreign rivals, we have no large and costly plants, erected on the Leblanc plan, which must be abandoned and exchanged for new but cheaper plants, before the ammonia-soda process can be adopted. 5. We have a constantly increasing demand for soda, which is almost entirely supplied by importation. If slow progress has been made hitherto in this country in the extension of this manufacture (only one plant at Syracuse, erected . under the Solvay patent, having as yet been placed in operation), I still feel gratified in saying that developments in England, and particularly on the Continent of Europe, give ample proof of the

Jan 1, 1885

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

By AIME AIME

ANNOUNCEMENT on August 6 of the historic event of dropping an atomic bomb on Hiroshima, Japan, was more dramatic even than V-E day, since that had so long been forecast whereas the bomb production had been the best-kept secret of the war, even though at one time more than 100,000 people had been at work in connection with its production, and some two billion dollars had been spent on the project. Mining men had long been aware of an unexplained abnormal interest in uranium production, and suspected that something of the sort was on foot, while metallurgists were aware that various men of their acquaintance were engaged in some top secret research. The first announcement was soon supplemented by other official releases which told more about the research laboratories for theoretical and pilot studies, and the plants in Tennessee and Washington, but none of them made clear what the modus operandi is of these terrific bombs. Inquiry at Colum. bia University, where Dr. Dunning and his associates had succeeded in 1939 in splitting the uranium atom, and where laboratories known only as SAM have been feverishly active since the beginning of the war, was unproductive, since none of those officially connected with the project could give out anything beyond the official releases.

Jan 1, 1945

By R. W. Raymond

Franklin Guiterman was born March 7, 1856, in Cincinnati, Ohio, where his father, William Guiterman, was at that time engagcd in the wholesale dry-goods business. Both of his parents were natives of Bavaria, but the inspiration of America was upon them, as they gave to their son a peculiarly American name, symbolizing thrift, individualism and scientific knowledge. Franklin Guiterman received his general education in the grammar schools and the Hughes High School of Cincinnati. He finished the latter course in the early 70&apos;s of the last century, when the great demand for mining and metallurgical experts in this country naturally led his parents to direct his further studies in that direction. Accordingly, he went to Europe, and studied at the Royal Saxon Mining Academy of Freiberg, where he completed the course in 1877, at the age of 21, and returned to the United States to engage in mining and metallurgical practice. Going to Colorado, he became assayer for the Terrible mine, at Georgetown, and in 1878, for the Little Chief mine at Leadville. The position of assayer, particularly at that period and in that region, was the door to much valuable knowledge of mines and ores. Besides learning the nature and value of the different classes of ore from the mines of his own company (if he was employed by a company) the assayer, had the first chance, through his outside customers, of seeing and testing the specimens brought by prospectors, and thus learning of important new discoveries. Moreover, if he possessed metallurgical knowledge, he might advance to the position of a metallurgical manager. Guiterman stayed in Leadville four years, and during that period was assayer or chemist for several different companies. Then for about a year he superintended copper-mining operations at Hartville, Wyo. In 1884, he had charge of sampling works at Silverton, colo.—an admirable opportunity for gaining wide knowledge of the varied ores of the San Juan country. In 1885, he was Superintendent of the Mingo plant of the Pennsylvania Lead Co., at Sandy, near Salt Lake City, Utah. The foregoing list of employments, each occupying not more than a year, certainly looks like the history of a rolling stone, gathering no moss. But the cause of these frequent changes was not inefficiency in each new position. In that time and period, a man who lost his place for such a reason was not likely to get another in the same neighborhood might away. And as for gathering "moss," the kind of "moss" that

Jan 1, 1918

By C. S. Smith, K. K. Ikeuye

In an earlier paper1 one of the authors called attention to the significance of the relative free energies of grain boundaries and interphase boundaries in alloys in determining the shape and distribution of micro-constituents. The ratio of the interphase and inter-crystalline boundary energies (that is, —?12, where ?12 is the energy of the interface between a crystal of phase 1 and a crystal of phase 2, and ?11 is the energy of the boundary between two crystals of phase 1) will be denoted by F. It is this ratio that determines, by the simple triangle of forces relation, the dihedral angle, ?, of phase 2 where it adjoins a boundary between two grains of phase 1. On a metallographic sample various angles are actually obtained because of the random orientation of the plane of observation, but the statistically most frequent angle is the true one. These basic principles were discussed in detail in the earlier paper. The experiments described below show the effect of both composition and temperature on ? and T for some alloys containing a liquid phase, and provide data on the rate of approach to the equilibrium angles in both solid and liquid phases. All the alloys were melted in a graphite crucible and cast into ingots 3/4 by 11/8 in. cross-section. Some of the aluminum alloys consisted of two immiscible liquids from which uniform castings could not be obtained. The amount of liquid phase varied locally to a considerable extent and the analyses were meaningless. Nevertheless, the composition of the liquid would not differ from that in an alloy of the intended gross composition, and the synthetic composition of the alloys was therefore used in considering the surface energy results. The ingots were given initial deformation by cold-rolling to 50 pct reduction, annealed, and given a second 50 pct reduction prior to cutting into small samples for heat treatment at the times and temperatures subsequently reported. The resulting micro-samples were carefully prepared metallographically and examined at magnifications of 650, 1280, or 2500. The objectives used were 21X, 0.40 NA (dry); 41X, 0.65 NA (dry); and 80X, 1.40 NA (oil emulsion). The appropriate angles were measured by rotation of the stage of a Bausch and Lomb metallograph to align the appropriate boundaries successively with a cross-hair in a micrometer eyepiece. About 250 angles were measured on each phase. Though the angles were read to 1°, the accuracy is probably not above 3°, because of uncertainty in setting the cross-hair tangent to the sometimes curved boundary. The corners of very small particles, particularly in early stages of adjustment after cold-rolling, were difficult to measure and the results were slightly dependent on the magnification used (compare Fig 1-C and 1-D). With particles of larger size and more nearly equilibrium shape, magnification made no difference (vide Fig 1-F and 1-G). The measured angles were grouped in 10° intervals (5° if ? was less than 20°) and plotted in bar

Jan 1, 1950

By S.H. Ash, P.S. Miller

Extensive and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past I0 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the Succdeding face, constituting a round. Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons" tunne1ing is more hazardous than mining in any branch of the mineral industry. On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. The Delaware Aqueduct The new Delaware aqueduct is a Manhattan project of some magnitude; when regular it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1943

By P. S. Miller, S. H. Ash

Extensive and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past I0 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the Succdeding face, constituting a round. Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons" tunne1ing is more hazardous than mining in any branch of the mineral industry. On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. The Delaware Aqueduct The new Delaware aqueduct is a Manhattan project of some magnitude; when regular it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1943

By Alfred H. Brooks

PetRoleUm seepages are known in Alaska at four localities, all on Pacific seaboard. These, named from east to west, are Yakataga, Katalla on Controller Bay, Iniskin Bay on Cook Inlet, and Cold Bay on the Alaska Peninsula. Besides these, a petroleum residue has been found near Smith Bay on the north Arctic coast of the Territory. At Katalla, Cold Bay, and Iniskin Bay there has been some drilling for oil, and in the first field several productive wells have been opened up. Alaskan petroleum, so far as its composition is known, is a refining oil, with paraffin base and low sulphur content. Most of what is known of the geology of Alaska oil fields is based on the investigations of Dr. George C. Martin, of the United States Geological Survey. A, G. Maddren, of the same service, has recently made a reconnaissance of the Yakataga oil field. The data to be here presented are chiefly taken from the following publications: G. C. Martin: The Petroleum Fields of the Pacific Coast of Alaska, with an account of the Bering River coal deposits, Bulletin No. 250, U. S. Geological Survey, pp. 9 to 27 (1905). G. C. Martin: Geology and Mineral Resources of the Controller Bay Region, Alaska, Bulletin No. 335, U. S. Geological Survey, pp. 112 to 130 (1908). G. C. Martin and F. J. Katz: A Geologic Reconnaissance of the Iliamna Region, Alaska, Bulletin No. 485, U. S. Geological Survey, pp. 126 to 130 (1912). A. G. Maddren: Mineral Deposits of the Yakataga District, Bulletin No. 592, U. S. Geological Survey, pp. 143 to 147 (1914). Katalla Field The Katalla field is marked by a series of seepages and gas springs occupying an east and west belt, about 25 miles in length and from 4 to 8 miles wide. (See Fig. 1.) This zone skirts the north shore of Con-

Jan 1, 1915

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman&apos; have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By W. S. Hyler, W. L. Bruckart

The powder metallurgy and arc-cast types of wrought molybdenum stock were studied in rotating beam fatigue. Endurance ratios of unnotched specimens after 5x10 cycles were found to be 0.74 and 0.81, respectively. Fatigue notch factors (K,) of 1.36 and 2.05, respectively, were obtained on V-notched specimens having a theoretical stress-concentration factor Kt = 3.1. MOLYBDENUM and its alloys are rapidly gaining importance as engineering materials of construction for high temperature applications. AS a wrought material, molybdenum and its alloys are outstanding above 1800°F. It is necessary, however, with molybdenum to provide elevated temperature oxidation protection. This is currently being studied by a number of investigators. Thus far, there have been no published data on the fatigue behavior of molybdenum either at room temperature or at elevated temperature. The knowledge of fatigue behavior, particularly notched fatigue behavior, becomes increasingly important as the engineering importance of a material increases, especially from the design standpoint. The work described here was directed toward determination of the notched and unnotched rotating beam fatigue characteristics of molybdenum at room temperature. Also, it was desired to learn whether any difference exists between wrought molybdenum of the powder metallurgy and the are-cast types. Fabrication History of Bar Stock For this work, bar stock was procured from Climax Molybdenum Co. (are-cast type) and from Westing-house Electric Corp. (powder metallurgy type). The processing histories of these materials are listed in Table I. The first lot of are-cast molybdenum was deoxidized by aluminum additions. The second lot was deoxidized by carbon." Both lots of the powder Microstructure A microscopic examination of these materials, as received, revealed the powder metallurgy molybdenum to be free of inclusions and to be finely fibered. On the other hand, the are-cast C molybdenum possessed numerous carbide inclusions, and the arc-cast A appeared to have coarse grained fibers. These are shown in Fig. 1. Owing to the large apparent difference in fineness of fiber between the are-cast A and the powder product and are-cast C, a check was made of the recrystallized grain sizes to determine whether these differences persisted. A series of recrystallization anneals revealed mixed grain sizes in both the are-cast A and the powder product. Variations in grain diameter of as much as 50 times were found after full recrystallization at 1200°C for 30 min. There was no distinction between the two. Arc-cast C was not checked. Room Temperature Mechanical Properties Prior to subjecting the materials to fatigue tests, room temperature mechanical properties were determined. These data, together with the tensil: strength of the notched bars, data,togetherare listed in Table tensil: There were no significant differences in the tensile strengths of the two types of molybdenum. However, the powder metallurgy material was generally more ductile and yielded at a somewhat lower stress than the arc-cast material. Tensile strengths of the notched specimens indicated a slightly greater notch strengthening effect in the are-cast C than in the powder product, lot 2. Room Temperature Fatigue Properties Sample Preparation: Specimens were prepared for use in R. R. Moore rotating beam fatigue machines. These specimens had a continuous radius test section with a minimum diameter of 0.260 in. The specimens were prepared by grinding to shape and polishing to produce a smooth unworked surface. Polishing consisted of rotating a disk in the continuous radius section on which were attached, successively, emery belts of 240, 400, and 600 grit. The specimens were slowly rotated during the operation. The belt speed was high, and rotation was such that polishing scratches were longitudinal. Unnotched Fatigue Properties: Unnotched fatigue data were obtained from a number of specimens of each of the four lots of molybdenum. The results of the tests are presented in Fig. 2. From this figure,

Jan 1, 1956

By W. D. Robertson

SINCE the comprehensive paper of Moore, Beckin-sale, and Mallinson,&apos; little consideration has been given to the mechanism of mercury stress cracking of copper-base alloys, apart from extensive work on metallurgical and fabrication variables employing mercurous nitrate as an evaluation test. However, with the phase diagrams now available and the recent considerations of interfacial tension at grain boundaries, developed by Smith,2 it appears that the elements of a detailed solution to the problem are available. The facts that require explanation are: 1—Pure copper is not embrittled by mercury, with or without an applied or residual stress. 2—Cu-Zn and other copper-base alloys, in excess of some undefined solute concentration, are embrittled provided an external or residual stress is acting; cracking is not observed in the absence of stress. 3—The path of fracture is invariably intergranu-lar. 4—Copper and copper-base alloys do not dissolve readily in mercury at room temperature.&apos; Consideration of the Cu-Hg phase diagram% hows that, at room temperature, solution of copper in mercury is probably limited by the formation on the surface of a microscopically thin layer of inter-metallic compound, CuHg, having a very limited range of solubility which effectively restricts diffusion of copper and mercury. But, above 150°C (the highest peritectic temperature) copper solid solution is in equilibrium with a liquid Hg-Cu solution and, consequently, copper should dissolve freely in a large volume of mercury with the formation of an equilibrium dihedral angle at grain boundaries in contact with the liquid phase. Depending on the magnitude of this angle, mercury will or will not penetrate the solid phase along grain boundaries and spread over grain faces. Thus the measurement of the dihedral angle of grain boundaries in equilibrium with the liquid phase above 150°C should indicate whether copper is intrinsically resistant to embrittlement by mercury. In view of the fact that mercury is appreciably soluble in copper, it may also be anticipated that diffusion of mercury will take place at higher temperatures in the absence of the intermetallic compound and possibly at a more rapid rate along grain boundaries than through the grains, resulting in a Cu-Hg alloy of unknown properties. In the case of brass, the ternary system Cu-Zn-Hg is involved and, from the resistance of brass to general solution in mercury at room temperature, it is probable that a compound of limited solubility range also exists, similar to the binary Cu-Hg sys- tem. Also, compared with copper, a change in the dihedral angle at grain boundaries in contact with mercury may be expected to result from the addition of zinc to copper. The preceding generalizations appear to be confirmed by the following experiments. Experimental Results Oxygen-free copper wire, annealed at 700°C for 3 hr in copper foil, was immersed in mercury at 170°C, with and without an applied stress. After 24 hr immersion, specimens which were spring loaded to a nominal stress of 10,000 psi had not failed, and there was no apparent embrittlement as indicated by a 180" bend around a diameter approximately equal to the diameter of the wire (0.125 in.) : General solution of the surface had taken place, indicated by a change in diameter of the wire, and the resulting structure of the surface is shown in Fig. 1. It is apparent that angles have developed at grain boundaries and examination at a high magnification indicates that the angle is in excess of 120°, completely excluding penetration of mercury. In view of the measurements made by Smith n the

Jan 1, 1952