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By Hannon, J. W. G.

Silicosis is today's most important industrial disease and probably dates back to the Stone Age. Since the industrial revolution, increasing attention has been paid to those occupations where mineral dust is present in the air breathed by the workers. For many years it was assumed that the inhalation of all mineral dusts was hazardous. but investigations conducted in several countries pointed the statistical finger of guilt at free silica in any of its numerous physical forms as a dust of outstanding toxicity. Recognition of silica as the chief hazard has resulted in widespread use of the term "silicosis." Depending upon the concentration of finely divided silica dust to which the individual is exposed and the duration of exposure, silicosis may become a disabling condition in from one to thirty years. The structure of the lung and respiratory passages is such that only minute particles of silica can gain entry to the air cells in the lung (5 microns or under are most toxic). When these minute particles gain entry to the lung tissues they stimulate certain protective cells in the lung to multiply at an excessive rate. The cell's undergo inflammatory changes which result in nodular scars and a low-grade inflammation of the lung tissue. These progressive changes in the lung structure gradually encroach

Jan 1, 1949

By Charles Will Wright

FRANCE will be given a large portion of the Marshall Plan funds for relief, reconstruction, and industrial development in France and in her colonial possessions. At present that country is not in position to export any large tonnages of the mineral products needed in the United States. However, if, through Marshall Plan aid and private capital investment, production of these products can be largely increased, agreement should be made by which the United States is to get a substantial portion of such increased output in part payment for the material and technical aid they receive. France issued a decree, published in the "Official Gazette" on Feb. 3, 1948, which permits conversion into dollars of dividends derived from dollar investment in Government-approved projects and will agree to a scale of capital amortization to be determined in each individual case. This decree is to encourage private capital to cooperate with local capital in industrial undertakings. The French Colonial Ministry has prepared an extensive program for aid to the mining industries in overseas possessions to be undertaken by

Jan 1, 1948

By R. W. Mancantelli, J. R. Woodward

IN 1947 a large low grade deposit of uranium was located in the northwest corner of Saskatchewan, in the Beaverlodge property of Eldorado Mining & Refining Ltd. Most of the values occur as thin seams and as coatings on other minerals, and the ore, which is light and friable, is not amenable to the usual gravity methods of concentration. The acid leaching process developed to retreat the company's Port Radium tailings was also impractical, as the percentage of carbonates is high and the percentage of sulphides relatively low. Construction of the mill building and installation of equipment, both scheduled for 1952, awaited selection of a satisfactory ore dressing process on or before Oct. 1, 1951. An extensive research program on dressing of ores from the Ace mine therefore was undertaken by the Mines Branch in Ottawa, a research team at the University of British Columbia, and an ore dressing group at the company's Port Hope refinery. Pilot plant operations were conducted at the Ottawa plant of Sherritt Gordon Mines Ltd. under the general direction of C. S. Parsons, consultant on metallurgy and ore dressing for Eldorado. In mid-September, having compared results of the several research programs, Dr. Parsons recommended a process employing a carbonate or basic leach. He reported that, while the chemistry of the process had been proved, engineering of the flowsheet was incomplete, and he suggested that under normal conditions further pilot plant work at the Ace mine might be profitable. However, since this would involve a delay of 12 to 18 months in bringing the property into operation, he recommended that design of the concentrator proceed immediately. Concentrator capacity was determined by two considerations: 1) the amount of ore then available and 2) the expectation that continued improvements would be made in the ore dressing process as a result of the intensive research being carried out by the Mines Branch of the Department of Mines and Technical Surveys. As these improvements could affect both the chemistry and the en-

Jan 1, 1956

By Charles H. Moore

In the study of the properties of rutile pigments it became apparent several years ago that certain physical and optical properties could not be determined on particles of pigmentary size. Since reflected light is the dominant type which reaches the eye from small particles, the true color of pure rutile was not known. Most rutile pigments are acicular in habit, elongated parallel to the "c" axis. It was considered important to know the nature and tone of light transmitted, for example, by a basal plate. Further, as shown by spectrophotometric curves, there is a very strong absorption of light of 4000 k as measured on particles with random orientation. It would be interesting to see whether this absorption position varied with predetermined and selected orientations. Also, since the behavior of titanium pigments in a vehicle is important, a knowledge of the surface wettability of single crystals by various media should prove very fruitful. Finally, the optical properties of rutile are such that it should show, in a single pure crystal, greater fire and brilliance than the diamond. Mineralogists had long speculated that this would be the case and curiosity was strong to produce a single crystal large enough to cut.

Jan 1, 1949

By Hollis Peacock

THE Bingham area in the West Mountain mining district on the eastern slope of the Oquirrh range, some 28 miles southwest of Salt Lake City, has been the most consistent producer for the United States Smelting Refining and Mining Company, production having been continuous, except for minor interruptions, since the organization of the United States Mining Co. in 1899. This production has come from fissures and mantos largely within limestone members aggregating something less than 10 per cent of a thick quartzite sequence of Pennsylvanian age which has been warped into an open syncline plunging northwesterly. Bedding on the easterly limb dips 10°-45° but steep-ens to 90° and even overturns on the westerly limb. Ore bodies cluster about the more northerly of two elongate interconnecting stocks of monzonite which have risen in an axial position within this syncline. Largely within the more northerly of these stocks is the low-grade copper ore body exploited in the Utah Copper open cut of the Kennecott Copper Corp. The values, in seams, minute fracture fillings, and disseminations of pyrite and silica, pervade not only the stock but adjacent sediments, and form a nebulous, sprawling mass which both mineralogically and geographically is the center of the district. The more southerly of the twin stocks appears to be comparatively inert and without obvious relation to mineralization. which

Jan 1, 1948

By Herbert Hoover

THE Federation of Engineering Societies has been created for the sole purpose of public service. This initial meeting surely warrants some discussion of a few of the problems to which this organization, for expression of the --. engineering mind, can quite well give consideration. Some of the greatest of the problems before the country and, in fact, before the world, are those growing out of our industrial development. The enormous industrial expansion of the last fifty' years has lifted the standard of living and comfort beyond any dream of our forefathers. Our economic system under which it has been accomplished has given stimulation to invention, to enterprise, to individual improvement of the highest order, yet it presents a series of human and social difficulties for the solution of which we are groping. The congestion of population is producing subnormal conditions of life. The vast repetitive operations are dulling the human mind. The intermittency bf employment due to the bad coordination of industry, the great waves of unemployment in the ebb and flow of economic tides, produce infinite wastes and great suffering. Our business enterprises have become so large and complex that the old personal relationship between employer and worker has to a great extent disappeared. The aggregation of great wealth, with its power of economic domination, presents social, economic ills which we are constantly struggling to remedy.

Jan 1, 1920

By H. B. Kinnear

THE first copper stool used under an ingot mold to receive molten steel has recently been taken out of service after it had received ingots amounting to 6012 gross tons. This stool, weighing 8330 lb. had been in continuous service for 1822 heats since its installation. From this modest beginning the use of copper for ingot-mold stools grew to 425,000 lb. in 1934, with an additional 50,000 lb. of copper used in the form of inserts in cast-iron stools. During 1935 the quantity of copper used for stools increased by about 350,000 lb., making a total of 775,000 lb. now in use for that purpose. Copper used for inserts has increased during this time 180,000 lb., or over 350 per cent, to a total of 230,000 lb. The total of copper, therefore, in use at present under ingot molds is slightly over 1.000,000 lb.

Jan 1, 1936

By Wm. E. Milligan

DESPITE the zero weather of Monday, the morning meeting on nonferrous ore-reduction metallurgy got under way promptly under the efficient control of Arthur A. Center. The first and third portions of the paper on the Tri-State region were presented by B. M. O'Harra, with R. H. Lowe substituting for co-author Illidge on the second part. Attention was drawn to the compact design attainable when "Sink and Float" was employed as a means of primary concentration. The teaching profession should welcome this concise correlation of data from such a renowned center of lead and zinc production. H. R. Hanley and C. R. Hay¬ward were much interested in the mechanics of charging, manufacture, and life of the retorts.

Jan 1, 1943

By R. S. Newlin

IN reality, the Butte district is the birthplace of the Anaconda Copper Mining Co., for it was here that strength was gathered and means provided for later expansions of the Company. The Butte district was organized at a miners' meeting on Aug. 20, 1866, primarily for gold placer-mining operations. Substantial amounts of placer gold were recovered from gulch gravels during the period 1862 to 1868. The earliest lode claim locations in the district were recorded in July and August 1864. Copper ore was first shipped, to Swansea, Wales, in 1866. In November 1866, according to the Montana Post, construction of a smelter was started to treat the silver

Jan 1, 1948

By Thomas T., Read

THE education of adolescents to perform the duties and assume the responsibilities of maturity has been a characteristic of human society since the dawn of history. In the beginning the members of the immediate family performed this function, and in modern life they still have an important part in it. Possibly religion was the first field in which education began to be functional; young people were sent for instruction to a teacher who had a broader and deeper knowledge of the subject than was possessed by the family. It does not seem necessary for our purpose to attempt to determine how, when, or where instruction in the practical arts first' began to become functional, and the brief outline which follows must suffice. The discovery and utilization of mineral substances to improve and maintain the conditions of human living is a practical art, which must have had an almost accidental origin and have been developed by empirical experiments. We do not know, nor would it be useful to try to fancy, how men first learned that they could make use .of mineral substances to their benefit, but how- ever that knowledge was initially gained it was certainly trans mitted through instruction in the family. At first such activities must have been merely a .minor part of the making of a-living, but in time those who excelled found it better to devote them-

Jan 1, 1941

By S. F. Emmons

Jan 1, 1899

By Claude P. Heiner

mountain region to M tht Coast points for domestic consumption and for export are shown in Table 11. There is considerable disparity in rates from both Rock Springs, Wyo., and Castle Gate, Utah, to the four coast cities where the slack coal is to be used for purposes other than export. The rate on coal to be exported is the same from either starting point to any of the four coast cities even though there is a difference of as much as 341 miles in the shipping distance. It is interesting to note that the freight rate between Sunnyside, Utah, and Fontana, Calif., on coking coal is $5.05 per ton and that coal up to 8 in. can be moved on this rate if it is suitable for coking. This rate was published late in 1942 on a contemplated annual movement of more than 500,000 tons. There have been decreases in freight rates since 1923 on movements of slack coal from Utah into Seattle and Portland due to pressure on the railroads and to greater. quantity of coal shipped. It is the author,', opinion that a movement of slack coal in excess of 3 million tons of coal per year from Utah to any point in central California would justify a freight rate equal to that puhlished for Fontana, Calif.. or $5.05 per ton. The movement of 3 1/2 million tons of coal per year on the basis of 240 mine working days per year would require that 14,600 tons be handled each mine working day. If it is assumed that shipments could be arranged for a 6-day week, the average railway movement would he 11,200 tons, or approximately 3 trains containing fifty-five 70-ton coal cars per day. Such movements of coal would require railroad equipment represented by the investment amounts stated in Table 12 and entail the services of 250 men. Table 12 ... Railroad Equipment and Investment Required To Move 11,200 Tons of Coal a Day from Utah to California Railroad Equipment Cost 2800. 70-ton coal cara at $6.000 each $16,800.000 32 locomotives at $310.000 each. 9.920.000 Miscellaneous eauiument:.......... .5;000:000 Total........................ $31,720,000 It therefore appears that, under presently known mining methods, the lowest price at which coal could be sold f.0.b. the mine in amounts of 3 1/2 million tons per year for generation of power in central California would be $4.60. It also appears that the lowest freight rate that could be expecled between intermountain points and the central California area would be $5.05 per ton, making a total cost of coal delivered at a plant site of $9.65 per ton. Conelusions The following are the author's conclusions: 1. Coal mines in Utah and in the Kemmerer and Rock Springs districts of Wyoming could increase annual production by 6 1/2 million tons per year. 2. Under present conditions coal could probably be delivered to any steam electric plant in central California at a price not to exceed $9.65 per ton. 3. The use of coal at such a price, while higher than the equivalent present price of fuel oil, is entirely feasible. 4. There are adequate railroad facilities for movements of large quantities of coal from the intermountain region to the Rest Coast. 5. In a national emergency it probably would be extremely difficult, if not impossible, to obtain sufficient oil to meet requirements of the greatly expanded West Coast steam electric generatsing capacity. 6. The intermountain region contains ample coal reserves to supply all conceivable demands for West Coast power generation for a number of generations. 7. Increasing demands of labor threaten to lessen, if not eliminate, savings in cost of coal production through the use of new mining machinery. 8. Continuation of experiments in socialism by the Federal Government through construction of hydroelectric generating plants, particularly those unrelated to land-use reclamation, defies justification. Rates under this concept of a governmental function are subsidized through greater taxation of its people. Private capital is available to construct steam plants, or hydro plants where feasible, and should be permitted to continue in order to preserve the principles of our free enterprise system. DISCUSSION (L. C. McCabe and Robert P. Koenig, presiding) C. C;. BALl*—I was asked to lead off the discussion, but it is not with the thought that I might be able to add anything to the paper. The thoroughness with which it was prepared rather forestalls the asking of many questions. Your treatment, Mr. Heiner, is a very valuable contribution. I do want to suggest—that although you have limited your study to this specific question, with certain geographic limitations, many of the things in your paper apply just as well to the eastern coals. I want to agree 100 pct with your final conclusion concerning government-subsidized construction. Id. C. McCabe*—It is certainly worthwhile to take stock occasionally to see where we are going in problems of this nature. I agree with Mr. Heiner that ultimately the only reliable source of fuel that the West Coast has is coal hut the time factor is the difficult element to evaluate. Just before I came here I discussed this subject with N. B. Hinson, Vice President and Executixe Engineer of the Southern California Edison Company, and Chairman of the West Coast Inter-Power Exchange Committee. He has given much thought to utilities' fuel supply and it was very helpful to me in preparing a discussion of the paper to talk with him beforehand. Stock taking and forecasting of future development are essential to the continuing success of any enterprise. Mr. Heiner has called attention to the unprecedented growth of central and southern California and to the increased demands for fuel and power which have accompanied it. He discusses the increased fuel oil and natural gas requirements and the probable limits on the future use of these fuels and of hydroelectric power. In contrast to the calculable limits of these sources of electric energy, the author points to the availability of enormous reserves of coal in the Rocky Mountain States adjacent to the Pacific Coast which can be utilized for power generation. That there will be increased use of coal for power generation in the area under discussion is generally accepted hut it is in the timetable of such development that there is not complete agreement. In a recent report, Mr. Hinson reviewed the future power outlook for the Pacific southwest area. He pointed out that the use of steam plants in connection with water power plants in this region has made the maximum use of hydroelectric energy possible, and that the correct balance between hydro and steam generating plants produces the most economical overall system. Steam plants in the area which had been installed to protect against deficiency in hydro energy in dry years were used to carry war loads. Fortunately, no dry

Jan 1, 1950

By Hans Lundberg

IN last year's report on the progress of geophysics, the airborne magnetometer was the featured new development. At that time only a relatively small number of surveys had been made. During 1947, the airborne magnetometer was used in making many surveys and is again one of the high lights of the year in geophysics. This report is mainly concerned with geophysics as applied to the search for minerals exclusive of petroleum. In 194,5 and 1946, the use of the magnetic method reached a peak, partly because of an active period of prospecting brought on by an active mining market, particularly in Canada.

Jan 1, 1948

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a'. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex ' and not completely understood. It has been proposed that hardening occurs in some alloys' on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a' marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium' and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By O. N. Carlson, S. A. Bradford

Discontinuous yielding in tensile tests was observed in V-O alloys in the temperature ranges of 150° to 175°C and also 350° to 400°C. The magnitude and intensity of the serrations were found to vary considerably with oxygen content. Maxima were observed in tensile and yield strengths and in the strain-hardening coefficient at the higher temperature only. The strain rate sensitivity was observed to be negative between 150° and 400°C. THIS investigation was undertaken to study the effect of oxygen on the tensile properties of iodide vanadium in the temperature range of 25o to 450°C. Brown1 observed an increase in strength between room temperature and 400°C in vanadium metal, and found that oxygen and nitrogen had a rather pronounced effect on the strength and ductility. A maximum in the tensile strength was observed by Rostoker et al.2 near 300oC and by Pugh3 around 450°C for calcium-reduced vanadium. Pugh also found a maximum in the yield strength and in the strain-hardening exponent, and minima in the elongation and strain rate sensitivity at the same temperature. Eustice and Carlson4 reported the appearance of serrations in the stress-strain curves between 140° and 180°C in iodide vanadium containing 600 ppm O. These anomalies in the mechanical properties indicate that strain aging occurs in vanadium, but the impurity or impurities responsible for the above-mentioned effects have not been identified. The phenomenon of strain aging is usually characterized by the return of the yield point after interruption of a strength test. In the temperature range where strain aging occurs, the yield and tensile strengths attain maximum values, elongation and strain rate sensitivity exhibit minima, and discontinuous yielding is generally observed in the stress-strain curve. Cottrell5, 6 has postulated that strain aging is due to the migration of solute atoms to dislocation sites to produce locking after the dislocations have broken free from their impurity atmospheres during the initial yielding. At the strain-aging temperature the process is a dynamic one in which the solute impurity atoms diffuse to the vicinity of the moving disloca- tion producing "locking" which gives rise to maxima in the tensile strength and serrations in the elongation curves. Cottrel17 has noted that discontinuous yielding in iron occurs when the diffusion coefficient of nitrogen, D, and the strain rate, i, are related by D = 10-9 €. EXPERTMENTAL PROCEDURE The vanadium metal employed in this study was prepared by the iodide refining process as described by Carlson and owen.8 A representative analysis of the vanadium used in this investigation was: 150 ppm O, <5 ppm N, <1 ppm H, 150 ppm C, 150 ppm Fe, 70 ppm Cr, <50 ppm Si, 30ppm Cu, 20 ppm Ni, <20 ppm Ca, <20 ppm Mg and <20 ppm Ti. Alloys containing from 200 to 1800 ppm O, all of which lie in the solid solution range of the V-O system, were prepared by arc melting vanadium together with portions of a high-oxygen master alloy. The master alloy was prepared by tamping pure V2O5 into holes drilled in a vanadium ingot and arc melting this five or six times in an inert gas atmosphere, inverting the button between each melting step. The oxygen content of the master alloy was then determined by vacuum fusion analysis. Vanadium containing less than 150 ppm O was prepared in the following manner. A bar of iodide vanadium was deoxidized by sealing it in a tantalum crucible with a few grams of high-purity calcium. This was held at 1100°C for 4 days to allow time for the oxygen to diffuse to the surface and to react with the calcium vapors. The calcium oxide product was later dissolved from the surface of the bar with dilute acetic acid. In this way vanadium containing from 20 to 50 ppm O was prepared. Sample Preparation. The are-melted ingots were cold swaged into 3/16-in. diam rods and these were machined into cylindrical tensile specimens with a reduced section of 1.00-in. length and 0.120-in. diam. The test specimens were annealed for 4 hr at 900°C in a dynamic vacuum of mm of Hg to remove hydrogen from the metal. This recrystal-lization treatment produced a uniformly fine-grained structure with a mean grain size of approximately 0.06-mm diam. The oxygen contents reported in this paper were determined by a vacuum fusion analysis of the tensile specimens after testing. Analyses for other interstitial or metallic impurities showed no significant changes from that of the original material. Tension Tests. Tension tests were performed on a screw-driven tensile machine at a constant cross-head speed of 0.01 in. per min. Tests at elevated temperatures were carried out by heating the

Jan 1, 1962

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony&apos; states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By E. Klar, A. B. Michael

Differences in the electrical conductivities of copper powder sintered under reducing, selectively oxidizing, and neutral atmospheres are related to impurities in solution or as precipitated oxides. The precipitation of impurities as oxides during sintering in nitrogen is proposed for maximizing the conductivity of sintered copper. Conductivity equations for two-phase systems are summarized. Selected equations are applied to porous sintered copper and composite structures. A recent review of the influence of impurities on the electrical conductivity of copper by Gregory et al.1 emphasized that an impurity in solid solution has a much more pronounced effect on reducing the electrical conductivity than when present partly or wholly as a second phase. When impurities in solid solution can be precipitated as oxides, the copper is purified with respect to these elements and the conductivity is increased. Cast and wrought copper, therefore, frequently contain an intentional residual oxygen concentration to oxidize and precipitate impurities less noble than copper. Copper powders generally also contain impurities which can contribute to a reduction in the electrical conductivity of the sintered material. The most deleterious impurities commonly found in commercial copper powders which markedly decrease the electrical conductivity when in solid solution but which can be precipitated as oxides include iron, tin, antimony, arsenic, cobalt, and nickel. In addition to impurities, porosity in sintered copper also contributes to a reduction in the electrical conductivity. The work reported herein discusses the influence of impurities, sintering atmospheres, and porosity on the electrical conductivity of sintered copper. These are important factors for controlling the electrical conductivity of materials such as sintered copper electrical contacts. Several publications on the electrical conductivity of sintered copper and composite materials with random pores or obstacles have incorrectly considered the conductivity to be proportional to the volume fraction of conducting material. However, analyses and equations have been proposed, the earliest of which is perhaps Lord Raleigh&apos;s of 1892,&apos; which more accurately describe the conductivity of two-phase systems. These equations which in many cases allow one to closely estimate the electrical conductivity of porous sintered materials and two-phase composites will be reviewed and related to the measured electrical conductivity of sintered copper, copper-graphite. and Ag-W composites. INFLUENCE OF IMPURITIES AND OXIDIZING, REDUCING, AND NEUTRAL ATMOSPHERES Zone-Melted and Leveled Copper. The electrical conductivities of an electrolytic copper and a lower-purity compacting grade of copper powder after consecutive treatments in reducing or selectively oxidizing atmospheres are compared in Fig. 1. The powder and drillings from the electrolytic copper ingot were melted and solidified in a graphite crucible under hydrogen. The vertical zone leveling technique of multiple passes in opposite directions was used to obtain a uniform distribution of impurities. The electrical conductivity was measured on machined specimens 3 by 0.10 in. diam of the zone-leveled material and after the same specimens were consecutively treated as follows: 1) heating in hydrogen at 1600°F for 3 hr; 2) heating in air in a sealed tube so that 0.04 pct 0 was introduced; heating was started at 1000°F for 1 hr and continued at 1800°F for 8 hr; the stepwise diffusion treatment was used to avoid loss of copper due to evaporation of copper oxide at higher temperatures; and 3) final heating in hydrogen at 1600°F for 3 hr. A L&N Kelvin Bridge, type 4306, and a test fixture with knife edges 2 in. apart were used to measure the room-temperature conductivity with an estimated accuracy of ±0.5 pct. In all cases the conductivity of the electrolytic copper was approximately 100 pct of IACS. The conductivity of the impure copper was 80 pct of IACS both in the cast state and after heating in hydrogen. However, after the heating in air, the conductivity of the impure material was 100 pct IACS. After again heating in hydrogen, the electrical conductivity decreased to 60 pct of IACS. This decrease is attributed both to the dissolution of impurities and observed intergranular cracks due to the phenomenon of hydrogen embrittle-ment in copper. These data show that the electrical conductivity of commercial copper as represented by a compacting type powder can be increased significantly by the precipitation of impurities as oxides through heat treatment in an oxidizing atmosphere. Sintered Copper Powder. A commercial compacting type of copper powder pressed to various densities was sintered either in nitrogen, dissociated ammonia, or dissociated ammonia followed by a selectively oxidizing atmosphere of air in sealed Vycor tubes so that 0.06 pct O was added to the material. The electrical conductivity was measured perpendicular to the pressing direction on as-sintered specimens of approximately 3 by 0.25 by 0.15 in. The fully dense material was obtained by zone melting and leveling

Jan 1, 1969