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By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By Edmund J. Korber, Donald E. Raab, Frank A. Burns

During the early 1960s, the advent of self- advancing longwall roof supports triggered serious consideration by Bethlehem management to introduce the technique of longwall mining at one of our central Pennsylvania coal mines. Although longwall mining was initially justified as a means to cope with the severe roof conditions at our Mine 32 (Watson, B., 1971), the result of the endeavor has been a consistent and reliable level of coal production, first from Mine 32 and then later from Mine 33, over a period of fifteen years. Longwall production from the Cambria Division has been the mainstay of the low volatile coal required by Bethlehem Steel for steel production. Let us review the events that led to this accomplishment, as well as where we stand today.

Jan 1, 1981

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By P. R. Bradley

NO thought had been given to deep level mining at the Alaska Juneau mine prior to 1930, but in that year a prospect winze was started and continued for 1000 ft. vertically below the main haulage or adit level. The point at which this winze was started was selected entirely by the prevailing physical conditions, such as proximity to established workings, convenience, and the presence overhead of a substantial pillar of dimensions sufficient to lo¬cate the sheave wheel and loading pocket. It was, therefore, with some surprise that the unusually high-grade ore found just below the collar of the winze persisted, with certain vari¬ations, to a full depth of 1000 ft. vertically. Likewise this unusually high-grade ore was found to persist on the various crosscuts driven on levels at 200-ft. vertical intervals. To be brief, this deep level work found richer ore than any yet found in the mine over like areas, and inasmuch as the area was sufficient to plan for extensive deep level mining, plans for such work were given extended consideration.

Jan 1, 1936

By M. B. Kasen

eralized strain equation appear quite different they are really identical. This identity can be shown in a simple mathematical rearrangement. Referring to Eq. [I], the substitution of ln(1 +?E) for ? (where ?E is the engineering strain) yields: a =s8- (s8?so)e?1/?c) ln(1 +s8??E) [4] or s =s8?(s8?so)(l +?E)-1 [5] Replacing (1 + cE) with its equivalent, (l/lo): s=s8?(s8?so)l/€c [6] Adding and subtracting the quantity (s8 - so) yields: s=s8?(s8?so)+ (s8-so) l-(^)l/£c [7] = s0+(s8?so)ri-(^0)1/^l [8] Letting n = 1/?c it follows that: This equation will be seen to be identical to the generalized strain expression in Eq. [3], the coefficients a and b being equal to so and (s8?so)/?c or n(s8?so), respectively. Confirmation of the relationship noted above was provided by fitting experimental stress-strain data5 for 304 stainless steel (total strain from 0.072 to 1.15) at room temperature at a true total strain rate of 4 x 10-3 sec-1 to Eqs. [I] and [3]. In this study nonlinear regression analyses were used to evaluate the equation constants. The results of this evaluation are presented in Table I. When these constants are used in Eqs. [I] and [3] the curves obtained are coincident. It will also be noted that the value of n is equal to YE,, the value of a is equal to so, and the value of b is equal to (s8 - so)/Ec. These equalities are illustrated in Table I where the Voce constants in parentheses were calculated from a, b, and n values. Excellent agreement is seen to exist. It is concluded, therefore, that the Voce equation is, indeed, identical to the linear expression involving generalized strain. In applying the generalized strain concept to stress-strain data, it has been noted3 that data within what was termed the transition region (first few points in the plastic flow region) must be excluded from the analysis in order to obtain the linearity in Eq. [3]. A similar exclusion applies in the use of the Voce equation since an expression which would describe the strain-hardening region would usually be found to be not too effective in the elastic-plastic fillet2 which connects the elastic line to the strain-hardening region. These considerations further substantiate that Eqs. [I] and [3] do indeed describe identical behavior. Note added in proof. Since this manuscript was submitted for publication, correspondence with Professor S. R. Davies, University of Edinburgh, (of Ref. 3) indicated that his associates have also confirmed the identity between the Voce equation and the generalized strain concept. It is sometimes desirable to obtain a small grain size in super-purity metals. Unfortunately, the absence of impurities, the low recrystallization temperatures, and the low activation energies for boundary motion result in rapid growth of relatively few grains when conventional recrystallization practices are used. For example, Arajs et al.1 were unable to obtain a mean grain diameter less than about 0.4 mm in iron containing 38 at. ppm of impurity. The <1 at. ppm purity range in many modern superpurity metals results in yet larger limiting grain sizes. It is the purpose of this communication to describe a technique by which mean grain diameters as small as 30 µ have been produced in aluminum having an impurity content < 0.5 at. ppm. The technique should be applicable to superpurity metals other than aluminum and has potential applications to grain refinement of commercial alloys. The necessary and sufficient requirements for production of a small grain size are as follows: a) a large number of potential nucleating sites must be created randomly within the cold worked material, b) sufficient thermal energy must be provided at a rate that will simultaneously activate a large fraction of the potential nuclei, and c) the grain growth must be stopped shortly after grain impingement.&apos; A high density of potential grain nuclei may be cre-

Jan 1, 1970

The co-operation of the. members of the Institute is earnestly sought by the Committee on Nominations, recently appointed by the Board of Directors, in its work of formulating a ticket for officers and places falling vacant in the Board of Directors in February, 1916. The Committee must present the official ticket of nominations to the Board of Directors at its October meeting. Members are, therefore, urged to send promptly their nominations for officers and Directors in order that the Committee may have an opportunity to give, them full consideration. The officers to be elected at the annual meeting in February, 1916, are: One officer, known as Director and President: Two officers, known as Director and Vice-President. Five officers, known as Director. The officers of the Institute whose terms expire are as follows: President, William L. Saunders (not eligible for re-election). Past President, Charles F. Rand. Vice-Presidents, Thomas H. Leggett, District 0; Fred W. Denton, District 4.

Jan 10, 1915

By Frederic Brunton

I. INTRODUCTION THE smelting plant of the British Columbia Copper Co. at Greenwood, B. C., now closed because of the decline in the price of copper due to the European war, is of special interest to metallurgists for several reasons. It was successfully smelting in blast furnaces the lowest grade copper ore of all plants in America. In order to do so, it had to run at&apos; very high efficiency, which necessarily required a large tonnage per square foot of hearth area, together with the minimum amount of labor and other costs. The furnaces smelted daily 2,250 tons of ore (6.62 tons per sq. ft. of hearth area), carrying 0.85 per cent. of copper, at a smelting cost of $1.18 per ton. The entire plant required 130 men to operate it and keep up repairs, showing a labor efficiency of about 17.5 tons per man per day. In the present paper, the method of obtaining these results is shown. Most of the information contained in this description I obtained as Assistant Superintendent, during the two years preceding the present shutdown. Other sources of information to which I am indebted are: The British Columbia Copper Co., Ltd., by Alfred W. G. Wilson, in The Copper Smelting Industry of Canada; Greenwood Smelting Works, by J. E. McAllister, Engineering and Mining Journal, vol. xci, pp. 1011 to 1015 (May 20, 1911); and Description of the Copper Smelter of The British Columbia Copper Co., by W. L. Bell, in Transactions of the Canadian Mining Institute, vol. xvi, pp. 151 to 154 (1913).

Jan 7, 1915

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By H. T. Hildage

ALTHOUGH Greater New York does not bear any resemblance to a great mining district, the mining operations that are being conducted in and about the city are both extensive and interesting in character. With regard to the extent, it may be mentioned that, at. present, there is more dynamite used in New York than in any mining district in the United States; that there are under construction about 38 miles of tunnel, and that 66 miles more are projected, most of which must be constructed in the near future ; that since 1902 at least 2,000,000 tons of earth has been removed in underground work, in addition to about 3,500,000 tons that has been removed in, open-cut in connection with tunnel-work, and many times this quantity that has been removed in excavating foundations for buildings not connected with tunnel-work; and that there are to-day probably more than 5,000 men engaged in mining-work in and about New York City. These undertakings include almost every operation connected with underground work, from exploration by means of trench and boring, to the sinking of large shafts and the driving of large tunnels through every kind of ground from hard rock to soft, semi-fluid silt and quicksand. It is proposed in this paper to give a general description of some of the methods and appliances used in the opening-up ,of a "mine" in a large city, and a brief description of some of the "mines" now being developed in New York, connecting as far as possible the methods described with the particular work for which they were designed, in order to give a general idea of the

May 1, 1907

By J. T. Ryan

POISONOUS, irritating, or explosive gases are found in almost every industry, and manufacturers of gas masks are called upon to provide gas mask protection for a great variety of conditions, such as operators in horseradish factories, fumigators of homes and ocean liners, and men engaged in the manufacture of tetra-ethyl-lead, the new motor fuel. The modern type of gas mask and respirator, to provide protection against all such industrial gases, is an outgrowth of the gas mask developed during the World War to protect the soldiers against the poisonous war gases. So far, it has been possible to develop ample mask protection from all known noxious gases and fumes present in atmospheres encountered in mines, metallurgical works, and chemical and other industries, so long as there is sufficient oxygen present to support the flame of an oil lamp. The most important development of the gas mask was in providing protection against carbon monoxide- which is the noxious gas that mining men are most concerned with and, in fact, is the noxious gas that man is most frequently exposed to. This paper will be con- fined largely to the discussion of masks for underground use in metal mines. Gases that contaminate the normal air in mines can be divided into two classes: those that are given off normally by the workings, and those that are produced in mine operation.

Jan 1, 1926

By AIME AIME

THE 122d meeting of the Institute was held in the Lake. Superior Copper and Iron Country Aug. 20 to Sept. 3, 1920 with an approximate registration of 1100 members and guests. This is the &apos;first visit of, the Institute to this vicinity since 1904 although previously it held meetings there every six or, seven years. &apos;The eastern party assembled at Buffalo and sailed on the S. S. "Tionesta ". on Friday morning, Aug. 20, arriving at Houghton, Mich., Monday, Aug. 23. En route stops were made at Detroit, where sightseeing auto trips were taken, and at Mackinac Island, where a short stop permitted a visit to the picturesque and historic Fort Mackinac.

Jan 1, 1920

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.&apos; More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.&apos; This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.&apos; These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer&apos;s6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-&apos;. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.&apos; and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner&apos;s3 data for cation self-diffusion, D:, using Wagner&apos;s theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner&apos;s data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-&apos; at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper&apos; on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.&apos; In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.&apos; The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1&apos;9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By C. A. Fisher

THE Salt Creek Oil Field of Wyoming occupies a unique position among the major oil fields of this country. Many years before the beginning of actual production in this area, in 1911, it had attracted country-wide attention as a district holding oil possi¬bilities. Even foreign capital, mainly French and Belgian, had sought out this district as having oil values and spent many thousands of dollars &apos;in an effort to acquire property rights&apos; in this field which was very largely located on the public domain. Owing to inadequate laws governing the acquisition of oil lands on the Federal domain and a careless practice having grown up among oil land locators of that time, a complicated title situation quickly developed in Salt Creek. This condition of uncertain titles together with the isolation of the field from industrial centers were doubtless the two most potent factors in retarding its early development. After actual production began in 1911 governmental regulations, suits between the government, and the locator, disputed ownerships between locators and claim and counterclaim continued to retard the field&apos;s development. It is believed that the title situation in the Salt Creek Field, where potential values of such magnitudes were involved, was responsible more than any other factor for the ultimate passage of the government leasing act in 1920 affecting all oil lands on the Federal domain.

Jan 1, 1925

By F. H. Deily, D. S. Rowley, R. J. Howe

By B. G. Reisdorf

This paper describes the microstructural changes that occur when quenched ultrahigh-strength steels containing OA pet C and various amounts of nickel, silicon, and cobalt are tempered. The changes that occur in hardness, yield strength, and martensite diffraction-peak widths when these steels are tempered are related to the precipitation of the carbide phases. An unea$ectedly high silicon content (about 30 pct) was found in the E -carbide phase in a steel containing only 1.5 pct Si. TEMPERED martensitic steels have such wide-spread utility that they have been the subject of numerous investigations, and a sizable amount of literature has developed on this subject.M This investigation, which is a part of a larger program to correlate microstructure with mechanical properties at a variety of strength levels, is limited to the microstructural changes that occur when a quenched 0.40 pct carbon steel (USS Airsteel X-200 steel) is tempered, and to the effects of the alloying elements—nickel, cobalt, and silicon—on these microstructures. Used in this investigation were electron microscopy, electron-diffraction identification of the carbide phases, electron-probe micro-analysis of the carbides, X-ray determinations of retained austenite, and measurements of martensite X-ray diffract ion-peak widths. MATERIALS AND METHODS The chemical analyses of the eight heats examined eats No. 30 through 37) are shown in Table L Heat No. 30 has the chemical com~osition of Airsteel X-200, and the remaining seven heats contain various amounts of nickel, chromium, cobalt, and silicon. The heats were air-melted in an induction furnace and cast into 8 by 8 in. ingots that were subsequently heated to 2300 and rolled to 1-in.-thick plate. Oversize 0.505-in.-diam tensile specimens were rough-machined from the plates and austenitized in air at 1700° F for half an hour and oil-quenched. The specimens were then tempered in air at temperatures of 400° to 1000 for tempering times of 1, 4, and 16 hr, and finish-machined to 0.505-in.-diam tensile specimens. Electron micrographs were prepared from Formvar replicas of the midthickness of tensile-specimen shanks that had been electrolytically polished and etched in nital. Electron-diffraction patterns were obtained from carbon-extraction replicas. The replicas were prepared by etching the sample surface in the same manner as for microscopy, evaporating carbon on the etched surface, and re-etching the sample to free the carbon film and the precipitate particles. Electron-probe microanalysis was performed on some of the extraction replicas. To obtain adequate fluorescent X-ray intensities, several thicknesses of replica were exposed to the electron beam so that the results represent an average composition of the extracted particles rather than an analysis of single precipitate particles. The retained austenite contents of the specimens were determined by an empirical X-ray diffraction

Jan 1, 1963

By Sherwin F. Kelly

THAT gold ores occur in Georgia is a fact apparently not widely known outside of that state, yet in the last hundred years nearly $18,000,000 worth of gold has been mined there. The discovery of gold-hearing quartz was made in 1823 on the "Forty Acre Lot" (which now belongs to the Columbia Mining Co.), in McDuffie County, and about seven years later the first stamp mill on record was erected near there. In recent years Georgia&apos;s gold production has dwindled to an insignificant figure. However, with the increase in gold price, interest in this district has been revived, so an electrical geophysical survey was undertaken to aid in discovering new quartz veins, on a part of the Forty Acre Lot, the adjoining Hamilton mine, and the nearby Woodall property.

Jan 1, 1934

By Charles E. Lundin, Albert S. Yamamoto

The phase eqrtilibria of the binavy system, Nb-Al, weye established by metallographic, X-ray diffraction, hardness, and thermal-analysis techniques. Three intermediate phases were identijied, Nb3.41, Nb2Al, and NbAl,. The N6,Al and NbAl phases have extensiue ranges of solubility. The maximum solubility of aluminum in niobiuitz is 23.0 i0.5 at. pct (8.0 wt pct) A1 clt 1960" i 10°C. The maximumt solinbility oj niobiunz in alunzinutz is less than 0.3 i0.1 at. pct (1.0 tut pct) fib. The A&apos;h,Al and Nbgl interinediate phases forr peritectically at 1960° 1UcC and 1870" i 1U9C, respectively, zuhereas the NbAl, phase fornts congvuently fio11t the melt at 1605" 10°C. A eutectic reaction oc- The intent of an over-all research program was to develop niobium-aluminide-base coatings for refractory metals since these coatings exhibit useful high- curs at 57.8 i 0.5 at. pct (28.5 wt pet) A1 and 1500" 10°C between NbAl and NbAl3. The aluminum-rich region of the system has a peritectic reaction where liquid reacts with NbAL, to form aluminum solid solution. Structural and lattice -pavarneter data /or the intermediate phases were determined by X-ray diffraction analyses. An unusual transfov?nation having charactevistics of nucleation-growth and martensitic nleclanisils occurs on cooling the niobium solid solution in the region from 18 at. pct (6 wt pct) Al to 23 at. pct (8 wt pct) Al. The transfornzed product on rapid quenchirzg is an acicular NhAl. temperature resistance to oxidation. As a prerequisite, the phase equilibria of the system, Nb-A1, were necessary. A literature survey revealed that the phase-equilibria data reported by various investigators were rather incomplete and conflicting. Therefore a complete determination of the system was undertaken by the authors from 0 to 100 pct of solute addition.&apos; In 1959 Savitskiyz presented a tentative diagram which

Jan 1, 1967