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By Charles Luner

ALTHOUGH the kinetics of the atmospheric oxidation of tin have been studied,1-3 the kinetics in pure oxygen have not been reported. This note presents some results of the kinetics of the oxidation of tin foil in pure oxygen. The tin foil used in this investigation was 99.78 pct pure, the two major impurities being Pb (0.17 pct) and Sb (0.024 pct). The foil was degreased and air-dried prior to oxidation. The air-formed film was estimated by coulometric reduction4 of the surface oxides to be about 25A. The samples, which were in strip form and had a total geometric surface area of about 300 sq cm, were first evacuated at room temperature in an oxidation bulb to 1 X 10 -5 mm Hg and subsequently degassed for 1 hr at the temperature of the experiment. Spectroscopically pure oxygen was then introduced into the bulb. The rates of oxidation were measured by following the rate of pressure change due to oxygen consumption in a closed system, the volume of which was sufficiently large so that the pressure change during an experiment was 10 to 15 per cent of the total pressure. An oil-mercury manometer,5 with a sensitivity of 3 X x mm Hg (which corresponds approximately to 5 X 10 -7 gm of oxygen) was used to measure the pressure change. The oxidation bulb was heated by an oil-bath and controlled to within -10.3 C. The reproducibility of the rates was good, as determined by the coincidence of rates at 190oC for duplicate experiments. Fig. 1 shows the oxidation curves in the temperature range 168 to 211.5oC at 8 mm Hg pressure. The effect of pressure on the rate of oxidation at 190°C is also shown. The rate of oxidation was not markedly affected by changes in pressure in the range 4 to 9 mm Hg, except perhaps at the lowest pressure, 4 mm Hg, where after about 70 min there appeared to be a decline in the rate, as compared with the rate at the higher pressures. At the lower tem- perature, 168oC, and for short reaction times, it is difficult to distinguish between a linear relationship and a slight curvature in the oxidation rate. However, for longer times, there was a somewhat larger indication of curvature. The samples after oxidation were gold-colored in appearance. The oxide that was formed at 170°C was identified as a-SnO by reflection electron diffraction. This is in agreement with results obtained by other workers.6, 7 The rate data best fitted the logarithmic-oxidation rate law, w = K1n ln(1 + -t/to) [1] where w is the weight of oxygen consumed, t is the time, and K In, and to are constants. First estimates to were obtained according to the method of Taylor Thon8 and were then employed to obtain the best simuItaneous estimates of to and K In, that would fit the logarithmic expression. These estimates were found numerically, so that the residual variance could be minimized. The calculations were performed on an

Jan 1, 1961

By C. E. Morris, S. R. Pollack

Current -vo1tage -temperature characteristics were studied for Al-A12O3-Al, Au structures. The oxide film was grown by gaseous oxidation in an 0, glow discharge. The electron-transfer mechanism was identified as tunneling and the barrier heights and thickness were determined. It was found that the barrier height at the parent aluminum-oxide interface is 1.5 ev and the built-in vloltage with an aluminum counter electrode is 0.35 v. The growth mechanism of the oxide is also discussed and it is suggested that Mott&apos;s theory is not applicable in describing the growth. Discrepancies were observed in the detailed comparison of tunneling theory, based on a trapezoidal model, with the data, and several possible explanations are discussed. THEORETICAL analyses of electron tunneling from one nonsuperconducting metal to another through an extremely thin insulating film have been presented.1-6 These calculations relate the current density, J, to the voltage, V, between the two metals, and to the temperature, T. The results of these calculations indicate that the magnitude of J and the detailed shape of the J-V characteristic will in general depend most strongly upon such properties of the insulating film as the thickness, the dielectric constant, and the structure of the electron energy barrier profile. The experimental results of many7-11 workers have corroborated the main features of these calcu- lations and have in fact been used to determine properties of the thin insulating film. It has been demonstrated, for example, that the tunneling current formulation of simmons4 is adequate to describe the observed J-V characteristic over approximately 10 orders of magnitude of current. Furthermore, from these observations and analyses, insight into the nature of the A1-A12O3 (thermally grown) interface region has been obtained.&apos;&apos; The temperature dependence of the tunnel current has also been studied and, although a self-consistent set of tunneling parameters can be chosen to describe these data at low voltages (i.e., <0.5 v), the tunneling parameters are different from those obtained from higher voltage (i.e., of the order of 1 to 5 v) measurements." We have measured the effect of temperature and voltage upon the tunnel current at higher applied voltages and find that the theory is inadequate to describe all of the effects reported here. A discussion of the origin of this inadequacy is presented following a description of the samples used for these experiments, and the experimental results. SAMPLE PREPARATION Metal-insulator-metal structures were fabricated in the following way. A 99.999 pct A1 charge was used to deposit, in vacuo, thirty films, 2000Å thick, onto a 1 by 2 in. glass substrate (7059 Corning glass). Prior to deposition the substrate was glow-discharged for final cleanup and then baked at 200°C for 2 hr at a pressure of 5 x 10-7 torr. The pressure during deposition of the metal films was 2 X 10-6 torr and the deposition rate was 50 to 100Å per

Jan 1, 1965

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.&apos; Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-&apos;. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By C. K. Leith

IN telling the story of Canada&apos;s minerals many interesting and spectacular details will be passed over to permit pointing out some of the significant inter- national aspects. No country now has enough of all minerals for its own use. The problems of satisfaction of both national and world demands under these conditions have become international in scope, and history supplies no obvious solutions. The minerals of Canada are coming to play a prominent part in such problems. Production and Reserves In the last decade Canada has rapidly advanced in mineral production. In 1928 the total value of mineral products from Canadian sources reached 273 millions of dollars. Canada ranks first in production of nickel, first in asbestos, second in cobalt, third in gold and silver, fourth in lead and copper, and sixth in zinc.

Jan 1, 1929

By T. O. Breitling

Two significant problems In mill design are environmental control and cost reduction. Environmental control is predicted to be 5-10% of total plant costs in some parts of the U.S. Operating and design companies will assign this new "unit operation" a place in the early flow sheets. More advanced environmental control will add to both capital and operating costs, so mill designers will strive to reduce other costs.

Jan 1, 1970

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa May, &apos;71.. 1 3 2. Bethlehem, I&apos;s Aug., &apos;71.. 110 3. Troy, N. Y Nov., &apos;71.. 113 4. Philadelphia, PaFeb., &apos;72.. 117 5. New York, N. YMay, &apos;72120 6. Pittsburgh, Pa Oct., &apos;72.. 125 7. Boston, MassFeb., &apos;73.. 128 8. Philadelphia, Pa.*May, &apos;73.. 23 9. Easton, PaOct., &apos;73.. 27 10. New York, N. Y Feb., &apos;74211] [ ]

Jan 1, 1925

By J. Gordon Parr, M. J. Bibby

In addition to the (bcc) - (cph) transformation at 882°C a second distinct change of slope has been observed on a titanium cooling curve between 905" and 960°C.1,4 Duwez,1 commenting on work by McQuillan,2-4 attributed this arrest to contamination of the specimen with oxygen—a possibility that existed even at the reduced pressure of 10-5 mm Hg at which the experiments were conducted.

Jan 1, 1963

Brushy Creek mine is located near the center of a linear, 40 mile long belt of mineralization that extends south from St. Joe Minerals Corp.&apos;s Viburnum division. The mine area includes a segment of 5.4 miles long of this new mining region along which eight mines are presently operating. The geology of the area is relatively simple; the rock formations have not been disturbed through folding or extensive faulting.

Jan 7, 1973

By F. J. Darnell

SINGLE crystals of a-titanium are difficult to obtain because of the phase transformation at 882 °C in which the structure changes from the high-temperature body-centered structure ß to the low-temperature hexagonal close-packed structure a. Preparation of single crystals of a-titanium has previously been accomplished by a strain-anneal method which takes several days and is not generally reproducible. Single crystals as large as 5 mm

Jan 1, 1959

[ ] [LOCAL SECTION CODE (Numbers indicate Sections) No. Section LI Alaska L50 Adirondack L2 Arizona L58 Arkansas L84 Balcones L66 Billings Petr. L3 Black Hills L4 Boston L76 Caracas L5 Carlsbad Potash L6 Central Appal. L60 Central N. Mex. L7 Chicago L79 CIM-AIME Calgary L82 CIM-AIME Edmonton L8 Cleveland L9 Colorado]

Jan 1, 1961

By J. L. Christie

A recent case of failure of a-low karat gold alloy by stress-corrosion cracking is of interest because it illustrates a principle frequently overlooked: the relation between high residual stress and high yield point. The alloy contained Gold, per cent 39.6 Copper, per cent 51.1 Silver, per cent 5.2 Nickel. per cent 3. 1 Zinc, per cent 1.0 Tension tests on the alloy showed the following:

Jan 1, 1945

By Lyall Zickrick, R. S. Dean, F. C. Nix

The first attempt to establish an equilibrium diagram of the lead-antimony series was made by Roland-Gosselinl in 1896. This investigation classified the system as a purely eutectiferous one, with the eutectic at 12.5 per cent. antimony and 228" C. In the next year, Stead2 placed the eutectic temperature at 247&apos; C. The error in temperature made by Roland-Gosselin, however, has been perpetuated in the literature with a remarkable degree of persistency; this value was accepted by Campbell (1902), and Ewen (1910),3 and will be found in the last edition of Desch&apos;s3 Metallography (1922). Gonterman&apos;s investigation, made in 1907, was the most complete one available at the time .the present investigation was started. He concluded4 that the system was a simple eutectiferous one and placed the eutectic at 13 per cent. antimony and 247° C. Other investigations by Tammann (1907),5 Garbow (1909),6 Rudolfi (1910),7 Loebe (1911),8 and Leroux (1913)9 added little, if anything, to Gonterman&apos;s diagram. A number of investigations have been made of physical properties of the alloys. The electrical conductivity of the series was studied by Matthiessen (1860)10 and by A. W. Smith (1921);11 the thermoforce by Rudolfi (1910),12 and Pelabon (1923) ;13 the specific heat by Durrer

Jan 1, 1926

By George Stern

THE purpose of this investigation has been to study one method for making ordinary carbon steel by the powder metallurgy technique. This method con- [ ] sists of pressing and subsequently sintering an intimate mixture of iron powder and graphite in a suitable atmosphere to produce a steel. Two types of iron powder have been studied, electrolytic and reduced. The sintering of mixtures of loose carbonyl iron and carbon black for several hours at 1000° to 1100°C. (1830° to 2010°F.), followed by forging of the resultant ingots to bars, has been studied by Offermann.1 Trail&apos; has reported on the properties of hydrogen-reduced and electrolytic iron powders, both containing 0.5 per cent carbon. Methods for making steel bodies by powder metallurgy have also been sug- [ ] gested by Goetzel,3 who recommends the addition of steel powder of well-defined carbon content to pure iron powder, and Volterra,4 who suggests compaction and subsequent sintering of a mixture of steel powder, iron oxide and iron powder. Additional methods for making steel bodies by powder metallurgy have been reported in the literature by Koehring,5 Allen,6 Balke,7 Wulff,8 Boegehold,9 and others. 10,11,12 It is felt that the method of pressing iron powder and graphite, as described herein, lends itself best to production because of the lubricating action of the

Jan 1, 1946

By George J. Bancroft

INTRODUCTION. IT is unnecessary to repeat here the contents of many valuable contributions to this subject which have appeared in the Transactions and in the publications of the U. S. Geological Survey. As a basis for the further suggestions of this paper, the following are the most important: 1. The investigation of J. R. Don,1 showing the gold of certain Australasian veins to have been deposited by ascending solutions, and not by lateral secretion. 2. The theory of Prof. Posepny,2 distinguishing the vadose from the deep circulation, and ascribing the origin of certain classes of ore-deposits to ascending solutions of the latter class. 3. The theory of Prof. Van Hise,3 as to the underground circulation and the primary enrichment of veins thereby. 4. The paper of Prof. J. F. Kemp,4 showing that ore-deposits are largely the products of " expiring vulcanism." Many of Prof. Kemp&apos;s, ideas have been widely adopted by mining men. 5. The theory of secondary enrichment, so lucidly expounded by Mr. S. F. Emmons.5 This theory, dealing with, the rearrangement of ore-bodies after primary mineralization, has been generally adopted, and seems to me to have been as completely proved as the nature of the case permits. There are two facts which I think should be constantly borne in mind in formulating a theory of the genesis of ore-

Jan 1, 1913

By William L. Fink, H. R. Freche

This is the thirteenth paper of a series from the laboratories of the Aluminurrl Company of America presenting the results of investigations of equilibrium relations in aluminum-base alloys prepared from electro-lytically refined aluminum. The ninth paper, on The Constitution of High-purity Aluminum-titanium Alloys,&apos; presented a type of system that had not previously been encountered in aluminum alloys. Subsequent work has shown that there are several similar binary aluminum diagrams including that of aluminum and chromium. The present investigation was limited to the cxtreme alnminum end of the aluminum-chromium system. The first systematic investigation of the aluminum-chromium equilibrium diagram was carried out by Hindrichs.? The resulting equilibrium diagram with some imaginary additions suggested by Guillet3 is shown in Fig. 1. Recently Goto and D6gane4 investigated the constitution of aluminum alloys containing up to 32 per cent chromium, and presented the diagram that is reproduced in Fig. 2. Wide discrepancies in the two diagrams are evident. The following intermetallic compounds have been reported in the literature: A1Crl5,6 AlloCrlzSi,5 AlCr4,6 AlCr3,7 AlaCr.8 Preparation of Alloys and Chemical Analyses With the exception of sample Y4206, which will be described under Determination of Hyperperitectic Liquidus, the alloys were prepared from electrolytically refined alurninum% Of which the analysis is given in

Jan 1, 1933

By William C. Aitkenhead, John A. Jaekel

Uranium deposits in the Spokane Indian Reservation, as well as those around Mt. Spokane, are essentially low grade, much of the ore containing less than 0.2 pct U808. The Mining Experiment Station of the Division of Industrial Research, State College of Washington, has been engaged in intensive research on the amenability of these low grade ores to froth flotation. The results: successful flotation of autinite, chief mineral constituent. At the outset of this work the goal was a concentrate of 1 pct U308 with a 90 pct recovery from ores containing less than 0.2 pct U3O8. Most of the work has been done on argillite ore from the Midnight mine on the Spokane Indian Reservation. The goal has not been attained using this ore, but samples of the granite ore from Mt. Spokane yielded successful results. For example, a concentrate containing 11.2 pct U308 was produced from a Mt. Spokane high grade ore containing 1.27 pct U3O8 with a recovery of 97.8 pct. Another Mt. Spokane ore yielded a concentrate of 5.0 pct U3O8 from an ore containing 0.13 pct U3O8, with a recovery of 85 pct. This same ore gave a recovery of 93.5 pct when the grade of concentrate was reduced to 2.0 pct.

Jan 1, 1959

By B. Fagerberg, P. H. Fahlstrom

Crushing and grinding practice in Sweden follows closely the international pattern. Certain special circumstances, however, have had an influence on its development. Most mines are worked underground. These mines are either quite small or very large. Sulfide ores are commonly treated by custom milling and, apart from the cement industry, the rock species treated are hard and abrasive. Another important factor is the increasingly strict requirements placed on the mechanical condition of different products, especially lump ores and coarse iron-ore concentrates. Increasing requirements are being placed on the concentrate grade to suit the new steel processes. As a result, iron ore beneficiation has expanded considerably for the production of fine pelletizing concentrates. This applies especially to magnetite ores in the intermediate phosphorus range 0.1-1% P. In 1969, about 5.5 million tons of pellets will be manufactured. It should be pointed out, however, that fairly large quantities of coarse products are still being made at mills where the right conditions are available. Crushing and grinding is also of great importance in the production of rich concentrates at high recovery from sulfide ores. In fact, a large part of the development work on the concentration of sulfide ores has been devoted to the crushing and grinding processes. Boliden has played an important role in this connection.

Jan 10, 1969

By D. L. Luffel

This paper presents two main developments: (1) a short, constantly accelerated centrifuge method of measuring drainage capillary pressure properties of cores, and (2) a new analytic method of treatment of centrifuge measurements to obtain saturation-capillary pressure relations. Toward the first objective, a clever experimental method is presented which is certainly more rapid than previous centrifuge methods. Toward the second objective, a new analytic method is derived to eliminate the approximate method of Hassler and runner. The derivation of this new analytic method, however, appears to be in error. The new analytic solution is developed as Eq. 5 in Appendix A. At the beginning of this derivation, the average wetting phase saturation of a core is expressed as, where is the centrifuge angular velocity. Eq. D1.2 makes explicit the dependence of S and S upon The second equation shown in Appendix A expresses the relation between the three variables Since for a given porous medium the saturation is uniquely related to capillary pressure, the functional dependence of S upon P is trivial, i.e., Pc.ri does not actually appear. Thus, the function 5 (r, ) may be expressed as a new function, S*, of PC, , alone The author transforms the variable of integration in Eq. Dl through use of Eq. D2 and writes

Jan 1, 1965