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By Blake M. Loring

RECENTLY the S-curves for 30 to 40 alloy steels have been published.1,2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.20 percent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr. at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1 1/4 by 1/2 by 1/8 in. Wires attached to the samples were used for handling, instead of tongs, to avoid chilling. The specimens were heated at 845°C. for 1/2 hr. and quenched into constant-temperature salt baths held at various temperatures from 205° to 650°C. The time required to transfer the specimens was found to be about x 1 1/2 sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 21°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1941

By L. A. Wright, H. L. McKinley

PINE Creek mine of Union Carbide Nuclear Co. is some 23 miles northwest of Bishop, Calif., in the Sierra Nevada Mts. Office and mill are 7800 ft above sea level, the 1500 level portal is at 9300 ft, the A level portal at 10,800 ft, and the 3050 portal at 11,500 ft. Original claims were located in 1916, and the mine worked intermittently until 1936, when it was purchased by Union Carbide Corp. Since then the property has been operated continuously, except for two brief periods when operations were suspended because of manpower shortages. Mine production through 1956 amounted to 2,792,425 dry tons of ore.

Jan 10, 1957

By H. William Ahrenholz

The coal industry had another prosperous year in 1966. Since the turn of the decade, production has been climbing at an average rate of 6% per annum. Although the fast pace slackened somewhat, 1966 production showed a gain of almost 3 % over that of 1965. An impressive record can be drawn from the fact that output per man-day in 1966 was more than twice that of the early 1950's, and more than three times that of the early 1940's. And even though man-power requirements lessened, those men retained by the industry worked longer hours and benefited through higher hourly pay rates. However, cost to the customer increased a little. Such statements can only be made for a healthy industry -one that is constantly improving its efficiency. Coal currently provides more than 25% of the total U.S. energy output. About 50% of all U.S.- mined bituminous coal goes directly to the electric utility market. It should be noted that, now, well over one trillion kwh of electricity is generated annually. Dependence of the giant electric utility industry on coal is based on economy and an abundant, dependable supply of this fuel.

Jan 2, 1967

By Eckley B. Coxe

The subject of this paper will be treated as briefly as possible under the following heads : I. The latest designs of some of the machinery used at these collieries in the preparation of coal. 11. The means employed for elevating, conveying and transporting the coal and slate in and about the breaker. 111. The means employed for raising the coal from the mines to the top of the breaker. IV. The iron breaker as a structure. V. The preparation of the coal as effected in the iron breaker. A key to the plates and the letters and numbers designating different parts, will be found at the end of the paper. I. Preparing Coal. Anthracite coal as it comes from the mines is not marketable. The "run of mine" cannot, as in the case of bituminous coal, be sold. Anthracite, being very compact and practically free from volatile combustible matter, burns only at the surface, and it is, therefore, deemed important to have the lumps as nearly of a uniform size as possible, so that between them a large amount of surface will remain exposed to the action of the air without checking the draught too much, or allowing enough air to pass to cool the coal below the ignition-point, In other words, if the pieces of coal of the size of a chestnut and smaller are mixed with lumps of the size of an egg they fill the air-passages and prevent a free draught. It has long been recognized, therefore, that one of the most important points in preparation is to have a uniform sizing, and also to make as large a number of different sizes as can be produced without too

Jan 1, 1891

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 ?ABBÉ, MAX F., Prest., Abbé Engineering Co, 220 Broadway, New York, N.Y. '07 ? ABBÉ, PAULO., Secy.,Abbé Engineering Co., 220 Broadway, New York, N.Y. '07 *ABBOTT, CHARLES W., Min. Engr. Pioche, Nev. ?08 *ABBOTT, CLARENCE Chief EDgr., Iron Mines, Dic Tennessee Caol, Iron & R. R. Co., Bessemer, Ala. '04 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94

Jan 1, 1917

By A. Lee Barrett

The Maintenance Committee of the Coal Division of the American Institute of Mining and Metallurgical Engineers is presenting with this report the first of a series of cost comparisons which it plans to present the Institute. The plan is to assemble maintenance cost on all equipment connected with mechanical operations at the face of coal mines, to arrange these costs by districts, to make comparisons between districts, and within districts. This particular report covers data with respect to mobile loading machines, including both "on-track" and "off-track" equipment. It is anticipated—in fact, considerable data have already been accumulated—that next year complete maintenance costs by districts can he presented for complete loading units, including the various classes and combinations of on-track and off-track equipment. Data have also been collected with respect to some phases of maintenance methods and certain recommendations of the committee are included dealing with maintenance problems. In the assembly of these data more than 120 questionnaires were sent to operating companies throughout the United States. At the time the report was written 33 questionnaires had been returned with completed information and an additional group of companies had written that the information requested was not at present available but that they hoped to have such information available in the not far distant future. The replies as

Jan 1, 1947

By Richard Moldenke

A. E. OUTERBRIDGE, JR., Philadelphia, Pa. (written discussion).¬ The fact that iron castings improve with age has long been known. Many years ago the late Sir Frederick Bramwell, a distinguished engineer, formerly in charge of the metallurgical and gun-making department of the Woolwich Arsenal, England, determined to break up a large number of cast-iron mortars of an obsolete type that had been in stock for years. It was then reported to biro that it was found to be much more difficult to break these old gun castings under the "drop" than it was to break similar gun-castings recently made, under his own supervision; he changed the.. composition of the iron and still found that whenever castings made recently were broken up (on account perhaps of superficial defects) great disparity was observed in apparent strength between the old and new castings. Sir Frederick then made many other comparative tests, such

Jan 4, 1917

By A. Lee Barrett

The Maintenance Committee of the Coal Division of the American Institute of Mining and Metallurgical Engineers is presenting with this report the first of a series of cost comparisons which it plans to present the Institute. The plan is to assemble maintenance cost on all equipment connected with mechanical operations at the face of coal mines, to arrange these costs by districts, to make comparisons between districts, and within districts. This particular report covers data with respect to mobile loading machines, including both "on-track" and "off-track" equipment. It is anticipated—in fact, considerable data have already been accumulated—that next year complete maintenance costs by districts can he presented for complete loading units, including the various classes and combinations of on-track and off-track equipment. Data have also been collected with respect to some phases of maintenance methods and certain recommendations of the committee are included dealing with maintenance problems. In the assembly of these data more than 120 questionnaires were sent to operating companies throughout the United States. At the time the report was written 33 questionnaires had been returned with completed information and an additional group of companies had written that the information requested was not at present available but that they hoped to have such information available in the not far distant future. The replies as

Jan 1, 1947

NEW MEMBERS The following list comprises the names of those persons who became members during the period Mar. 1 to 15, 1914: Members ADAMS, JOHN H., Cons. Engr First National Bank Bldg., Birmingham, Ala. ALEXANDER, WILLIAM H., Miner 80 Maiden Lane, New York, N. Y. AUSTIN, EDGAR TAYLOR, Asst. Smelter Supt., Mond Nickel Co., Ltd., Coniston, Ont., Can. BAKER, DANIEL, JR., Asst. Treas., Standard Lime & Stone Co. 524 Equitable Bldg., Baltimore, Md. BALL, MAX WAITE, Geologist U. S. Geological Survey, Washington, D. C. BARREN, HARRY B., Supt. Blast Furnaces, Inland Steel Co., Indiana Harbor, Ind. BAUMANN, HENRY N., JR., Amalgamator 365 Lynn St., Seattle, Wash. BLACK,, THOMAS B., Min. Engr Care Vulture Mines Co., Wickenburg, Ariz. BRADT, HARLAN H 429 West 111th_ St, New York, N. Y.

Jan 4, 1914

By S. L. Tainter

This paper describes the nature of engineering and geologic services for the production stage and a review of pit design factors peculiar to the development period. The Mission pit has passed into the mining phase where development is of secondary importance; however: until the pit reaches its final size, development will be a continuing function occurring simultaneously with mining operations. The deposit occurs in an extensive zone of altered sedimentary rocks which have been fractured by three fault systems, flexed or folded, and intruded by monzonite porphyry. The deposit is a low-grade copper sulfide "porphyry" type orebody within a broad zone of pervasive hydrothermal alteration in sedimentary rocks.

Jan 12, 1965

By Scott Howard

MANGANESE being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Ar3 transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the Ar3 transformation occurs at a temperature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3 quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Ar3 point as falling to 0° C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer,2 using alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 percent for the manganese content at which Ar3 is depressed to 0° C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By John T. Norton, Robert J. Anderson

The purpose of this paper is to report evidence, regarding metal structures, that is contradictory to the amorphous-metal hypothesis of Beilby, and particularly evidence that is opposed to the proposition that a vitreous amorphous layer is produced by polishing a piece of metal. According to the theory of Beilby, which has been developed by Rosenhain and others, polishing a piece of metal greatly affects the condition of the metal at or near the surface polished, making that surface entirely different in character from the metal beneath. A vitreous amorphous surface film is said to be formed. The polishing process, on the basis of Beilby's explanation, is well known and does not require discussion here, but it is advisable to seek the precise meaning of the term "amorphous." According to Beilby, "amorphous means non-crystalline in the most intimate sense of the word; the molecules arc not marshalled in crystalline order and orientation." According to Rosenhain, the amorphous condition is that assumed by a metal when the crystalline arrangement is completely broken up so that the atoms exist in a state of disorderly arrangement similar to that which exists in the liquid state. Thus, from the point of view of the phase rule, the "amorphous phase" is regarded as being identical with the liquid phase. Amorphous metal is often likened to an undercooled liquid. A crystalline substance is one in which the atoms are arranged in space according to some definite repeating geometrical pattern. The existence of amorphous metal has not been definitely proved. The evidence offered here that amorphous metal probably does not exist is of a direct nature and is afforded by x-ray diffraction effects given by a number of metals and alloys when polished, cold-worked, and annealed. Considerable of the experimental work was carried out with substantially pure aluminum and the aluminum alloy duralumin, but many of the observations made on these materials were checked by similar observations on copper, iron, tin, zinc, lead, mild steels, and

Jan 1, 1925

By A. J. Griest, P. D. Frost, J. R. Doig

During the past 5 years, research directed toward the development of titanium alloys having improved strength-ductility relationships and heat treatability has been carried out at Battelle for the U. S. Air Force.1"3 In the course of this work, a method of heat treating ß-stabilized titanium alloys was developed which produced a wide range of useful properties.4 The heat treatment consisted of two steps: a) solution treating at temperatures in the a-ß phase region, and b) overaging at a lower temperature in the range 800°to 1100°F. Corollary to the alloy development work, research was conducted on the mechanism of the heat-treatment reaction. The investigations of Frost and co-workers on isothermal transformation in Ti-Cr5 and Ti-Mn8 alloys disclosed the existence of the transition phase, w, during the course of the decomposition of metastable ß phase. Subsequent work at Battelle7,8 'and at Case Institute by Brotzen and co-workerss further clarified the nature of the decomposition process. Beta decomposition was found to proceed by the following series of reactions: 1 2 3 4 a + Ti, My (in eutectoid systems). ßo, ßr, and ßU refer to ß phase of original, enriched, and ultimate alloy contents, respectively. Omega is a transition phase having a complex structure. 10-13 Step 4, of course, occurs only in ß-eutectoid systems. This paper presents data correlating transformation behavior with mechanical properties for the following alloys: Ti-8Mn, Ti-8Mn-2A1, Ti-4Mn-4A1, Ti-6Al-4V, and Ti-4Fe. The isothermal decomposition of ß in titanium-manganese alloys of similar composition has been investigated by Frost and coworkers8 and the effect of various annealing treatments on alloys in this system has been studied by Holden, Ogden, and Jaffee.14 The compositions Ti-8Mn-2Al, Ti-4Mn-4A1, and Ti-6A1-4V, were studied in the present work in an effort to define more clearly the effect of aluminum on the response to solution and aging treatments. Ogden, Holden, and Jaffee15 have invesitgated the effect of aluminum on the response of a similar alloy (Ti-8.8Mn-2.46A1) to annealing treatments, and Luini and Lee16 have made an exploratory investigation of the heat-treatability of the Ti-4Mn-4Al alloy. The Ti-4Fe alloy was studied as an example of a moderate1y active eutectoid system. Holden, Ogden, and Jaffee 17 have studied Ti-Fe alloys and have presented some hardness data for aging at 400°C for alloys of Ti-2.56, 5.01, and 7.35 iron after quenching from the a-ß field (750°C). EXPERIMENTAL PROCEDURES The experimental procedures generally used in the precipitation-hardening study are outlined in the following sections. Departures from these techniques are noted in the discussions of the individual alloys. Table I presents the nominal and actual compositions of the alloys studied, together with the swaging and rolling temperatures. In all cases, these temperatures were in the a-ß field and the microstructures consisted of an equiaxed a-ß mixture. Melting and Fabrication—Except for the commer-

Jan 1, 1960

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies', the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,' vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell' published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson' has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

Jan 1, 1910

Discussion of the paper of John H. Hall, presented at the New York. Meeting, October, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1247 to 1256. WILLIAM 'R. WEBSTER, Philadelphia, Pa.:-I would like to call ,attention to the fact that the results of the ordinary tension and bend tests do not always give us the information we want even if we figure out the amount of work done. You want a bending test of sufficient width and full thickness. In the case of eyebars, for instance, I have had experience with a 10- by 1-in. eyebar which gave perfectly good results in a full-size test of the finished bar. The 10- by 1.5-in. and 10- by 1.75-in. eyebars from the same heats-of steel were absolutely worthless in full-size tests. The narrow bending tests from all these bars gave good results. Bat after going into the matter fully, we found that if pieces about 3 in. wide and full thickness were used for the. cold bending tests, the heavier material would not stand this test, but failed. That is, in order to check the quality of the rolled bar you should have a wide piece of full thickness for cold bending, as the narrow pieces give misleading results. J. E. JOHNSON, JR., New York, N. Y. :-I would like to ask if there have been any tests made to compare the results of Charpy tests with the true dynamic test similar .to the Wohler test, except that the piece is subjected to a tensile or compressive stress and to alternating stresses in addition, at the same time. This seems to me to approach more nearly than any other test to the conditions of actual service. where the piece is under a fixed initial stress plus a highly variable and often alternating stress. Some tests were made on this plan in England within a year or two. The test piece was Subjected to either a tensile or compressive stress of known amount and simultaneously to alternating stresses in addition. Such a. test as this gives information which we cannot get by a tensile test or even from the tensile strength multiplied by an. elongation. Such tests, however, are exceedingly tedious and require long periods of time in order to obtain valuable results. If material could be subjected to these dynamic tests and the same material to the. Charpy shock test, and if some reasonable qualitative relation could be established between the results of the two tests, then we could assume that the shock test, which is so simple and easy to make, was a measurably accurate test of the dynamic qualities of the material. At present it does not seem

Jan 12, 1913

By E. I. Organick, B. H. Golding

A simple correlation is presented for the prediction of saturation pressures in condensate-gas and volatile-oil mixtures. Saturation pressure is related directly to the composition of the mixture with the aid of two generalized composition characteristics, B, the molal average boiling point, and W, the modified weight average equivalent molecular weight. The need for hydrocarbon equilibrium constants is entirely eliminated. Only the values of the two conlposition parameters need be obtained, and these are calculated in a simple and reproducible manner from the stream analysis of the mixture and the ASTM distillation for the heavy ends. The correlation is given .in the form of a set of 14 working charts in which saturation pressures, either retrograde dew points or bubble points, are plotted cs temperature, forming partial phase envelopes for mixtures having discrete values of the composition parameters, B and Wul. A locus of critical states on each chart intersects the partial phase envelopes, distinguishing retrograde dew point pressures from bubble pressures. A comparison Between experimental and predicted saturation pressures reveals that: the probable error of the predicted values, when considering the data as a whole (214 experimental points), is five per cent; for high gasjoil ratio condensate fluids (approximately 40.000 or more cu ft/bbl) the probable error is about 8 per cent. In either case, however, the probable error is comparable with the overall uncertainty of the data from which the correlation is derived. INTRODUCTION There is a present need for a simplified, yet reasonably accurate method for predicting upper phase boundaries of reservoir fluids. In the case of high gas/oil ratio fluids, namely the so-called highly volatile oils and the condensate gases, no simple method, accurate within 5 to 10 per cent, is now available by which bubble point and retrograde dew point pressures may be predicted. In order to calculate the upper phase boundary of a volatile reservoir fluid, using correlations now available, it is necessary to find and employ the proper K-values (equilibrium volatility ratios of the hydrocarbons in that fluid). This process of finding the Proper K-values usually involves a double trial and error computation. Since the K-values are in themselves dependent upon the composition of the fluid, their use in the calculation of a saturation pressure actually represents an unnecessary complication. The correlation described in this paper relates saturation pressure directly to the stream composition, entirely eliminating the need for K-values. The only data required to calculate the Stream composition are obtained from the customary low temperature fractional analyses of separator gas and liquidt and from the ASTM distillation of the c,+ fraction of the separator liquid. A considerable simplification in the procedure for predicting saturation pressures is thereby effected without significant loss in accuracy. BASIS FOR A CORRELATION Empirical relationships between the saturation pressure and the composition of the fluid in question have already been partially explored by one of the authors.V n particular, a relationship between the critical pressure for a hydrocarbon mixture and its composition was developed. The critical pressure is in reality a saturation pressure, as it repregents a limiting case either of a dew point or of a buhhle point pressure for any given mixture. It was found that the critical pressure may be correlated as a function of two generalized composition characteristics or variables. One characteristic expressed a molal average prop-erty, the other a weight average property of the mixture. Specifically, the molal average boiling point (MABP, or B as it

Jan 1, 1952