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By H. A. Hancock, L. M. Pidgeon

Equilibrium carbon monoxide pressures were measured over the reaction between chromium oxide and a number of solid ferrochromium alloys in the composition range 0.4 to 4.8 pct C and 0 to 49 pct Fe. Measurements were also made for the carbides Cr23C6 and Cr7C3 which agreed well with previous investigations. Between 1050°and 1400°C the pvessures varied from 0.1 to 56 mm and increased markedly with the iron and carbon contents of the alloys. The data were used to estimate the activity of carbon in the alloys and to calculate the equilibrium conditions for the decarburization of a useful range of ferrochromium alloys. WHEN ferrochromium is produced by the reduction of chromite with carbon in an electric arc furnace it invariably contains up to 10 wt pct C. For many purposes such as the production of stainless steel, it is necessary that the carbon content be as low as from 0.02 to 0.05 pct. Thus an important part of the ferrochromium industry consists of the production of low carbon ferrochromium. The classical Bessemer steelmaking technique cannot be used to oxidize low carbon contents in chromium and ferrochromium alloys without also oxidizing the chromium. Recently a new commercial process2-4 has been introduced for oxidizing carbon from high chromium content alloys which consists of heating the solid alloy with such oxidizing agents as Cr2O3, Fe2O3, or SiO2 in a retort at reduced pressures. By maintaining the carbon monoxide pressure below the equilibrium value for the system, the carbon can be removed as carbon monoxide without oxidizing the chromium. The equilibrium conditions for the decarburization of solid chromium carbon alloys have been determined by Boericke5 who measured the carbon monoxide pressure over the reaction between the various chromium carbides and chromium oxide. A typical reaction is shown below. Cr23C6 + 2Cr2O3 =u 27Cr + 6CO [1] These values are not applicable to the decarburization of commercial ferrochromium alloys which invariably contain major amounts of iron. The present investigation was therefore undertaken to measure the change in the equilibrium carbon monoxide pressure brought about by additions of iron to the Cr-C-0 system, thus extending the work of Boericke into the region of the production of low carbon ferrochromium. MATERIALS AND METHOD Materials. Measurements were made on two carbides of chromium, Cr233C6 and Cr7C3, and fifteen Fe-Cr-C alloys. The chromium carbides were made

Jan 1, 1963

By N. A. Gokcen, John Chipman

D. C. Hilty (Union Carbide and Carbon Research Laboratories, Niagara Falls, N. Y.)—This paper is a very nicely detailed analysis of a difficult problem. I would like to point out that the results that Mr. Crafts and I published a few years ago had no reference to activity, or anything else of a similar nature; our results were strictly empirical. It is quite gratifying that we now have a case where results involving activity coefficients and results derived from direct observations on actual steel melts are practically identical. When two different laboratories, working from two entirely different approaches, come out with results in such good agreement in their major significance, that is an achievement. It is something that was not possible 15 or 20 years ago. There is one question I would like to ask Dr. Chip-man. It has to do with a very minor point of disagreement in these results. When we reported the kink in the Si-O solubility curve I think you may recall that it came at the different temperature levels at about the order of 0.015 to 0.03 pct 0 and 0.03 to 0.07 pct Si—we also pointed out that we had difficulty in obtaining data at that level, although we finally did get some. I note in going through the data for the present paper, that there are no samples in those particular silicon and oxygen ranges. I wonder if that was purely accidental or was there a reason for it. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—Mr. Hilty, do you have any explanation for that discrepancy between Dr. Chipman's curve and your own Mr. Hilty—Our explanation for it at that time was that for some reason our system probably was not in true equilibrium with SiO, that is, in equilibrium with the silica crucible at that level. We did observe, however, that that was the level at which both the metal and the slag became saturated with SiO,. On the average, in studying inclusion formation in small ingots permitted to solidify normally from the molten state, we observed pure silica inclusions at silicon contents over about 0.05 pct and FeO type inclusions at silicon

Jan 1, 1953

By CHRIS A. HARTNAGEL

For the second consecutive year, the production of crude petroleum in New York has fallen below the 5,000,000-bbl. Mark that had prevailed previously since 1937. In 1945, the output totaled 4,658,000 bbl., a decrease of slightly more, than one per cent from the 1944 production. This total represents 2 per cent of the stripper-well production of the United States, which in turn is I 3 per cent of the total annual yield of the nation's petroleum.

Jan 1, 1946

By H. I. Smith

CONTENTS [PAGE Problems of Mining and Processing Mineral Aggregates (TP 1649, by NATHAN C. ROCKWOOD, Min. Tech., Nov. 1943. Discussion by H. I. SMITH, IRVING WARNER and the author) t Mica in War (TP 1749, by RUSSELL G. WAYLAND, Min. Tech., July 1944. Discussion by H. S. SPENCE) 3 Three Roofing-granule Plants in Pennsylvania (TP 1787, by RICHARD M. FOOSE, Min. Tech., Jan. 1945. Discussion by H. I. SMITH)5 Methods of Prospecting and Mining Optical Calcite in Montana (TP 1896, by E. W. NEWMAN, Min. Tech., Nov. 1945. Discussion by W. C. STOLL and FRANK C. ARMSTRONG, and the Glass Sand and a Glass Industry in Puerto Rico (TP 1939, by HOWARD A. MEYERHOFF and J. EARL FRAZIER, Min. Tech., Nov. 1945. Discussion by A. M. SHORT, the author and PHILIP The "Bonanza" Mica Operation of Purdy Mica Mines, Limited, Mattawsn Township, Ontario (TP 2154, by HUGH S. SPENCE, Min. Tech., March 1947. Author's supplement and discussion by JOHN A. BAKER, E. J. LINTNER, and the author) 7 Process for Manufacture of Dead-burned Magnesite and Precipitated Calcium Carbonate from Dolomite (TP 2155, by ROBERT D. PIKE, Min. Tech., March 1947. Discussion by 0. C. RALSTON and the author) 9] Problems of Mining and Processing Mineral Aggregates H. I. SMITH*-Mr. Rockwood has presented a very interesting paper on problems of the mineral aggregate industry in meeting specification requirements, which apparently are ever decreasing in tolerance. May I call attention to a method of mineral separation that may be of value in separating the flat aggregate particles from the more angular ones and possibly the soft particles from the hard. The method is the old Pardee spiral coal separator, extensively used many years ago in the anthracite region for separating rock and bone from anthracite coal.1 The success of the process depends on the relative coefficient of friction of the aggregate particles to be separated rather than on their relative specific gravity. The flat and the soft particles normally will slide more slowly and stay on the inner spiral until they reach the delivery spout at the bottom whereas the round and the angular pieces will work to the outer edge and fall off into a spiral of larger diameter. The capacity of the separator is increased materially by having three inner spirals, with a separate feed for each, on which the particles travel more slowly, and one outer spiral from which the more rapidly traveling pieces slide to the bottom. IRVING WARNER*-I have long been convinced that much of the equipment and methods developed for mineral dressing might be advantageously employed in the mineral aggregates industry, and more particularly in the production of sand and gravel. The two industries are not well acquainted with each other or their problems. They have separate trade publications. The difficulty with the situation is that there are few large sand and gravel plants and few provided with technical services in their own organization or by retainer. This does not refer to engineering organizations but rather to improvement of plant technic in processing.

Jan 1, 1947

By A. Paul Bond

Two series of 17pct Cr iron-base alloys with small, controlled amounts of carbon and nitrogen were vacuum-melted in an effort to detertmine the meclz-uniswls of inter granulur corrosion in ferritic stain-less steels. An alloy containing 0.0095 pct N aid 0.002 pct C was very resistant to intergranular corrosion, even after sensitizing heat treatments at 1700" to 2100o F. However, alloys containing more than 0.022 pct Ni and more than 0.012 pct C were quite susceptible to intergranular corrosion after sensitizing heat treatments at temperatures higher than 1700°F. This corrosion was observed after the usual exposure tests and after potentiostatic polarization tests. Electronmicroscopic examination of the alloys susceptible to intergranular corvosion revealed a small grain boundary precipitate; this precipitate was absent in the alloys not susceptible to such corrosion. Thc electronmicrographs indicate that intergranu1ar corrosion of ferritic stainless steels is caused by the depletion of chromium in areas adjacent to precipi-tates of chromium carbide or chromium nitride. It also seems likely that the precipitates themselves are attacked at highly oxidizing potentials. Confirma-tion of the proposed mechanisms was obtained in tests on air-melted ferritic stainless steels containing titanium. The titanium additions greatly reduced susceptibility to intergranular corrosion at moderately oxidizing potentials but had no beneficial effect at highly oxidizing potentials. A major obstacle to the use of ferritic stainless steel has been their susceptibility to intergranular corrosion after welding or improper heat treatment. It appears that sensitization of ferritic stainless steel occurs under a wider range of conditions than for austenitic steels. In addition, a greater number of environments lead to damaging intergranular corrosion of sensitized ferritic stainless steels than to sensitized austenitic steels. The chromium depletion theory of intergranular corrosion is widely accepted for austenitic stainless steels'" although there: are some objections.3 On the other hand, several alternative mechanisms proposed for ferritic stainless steels include precipitation of easily corroded iron carbides at grain boundaries,' grain boundary precipitates that strain the metal lat-tice,5 and the formation of austenite at the grain bound-arie.6 The application of the chromium depletion theory to ferritic stainless steels has been discussed extensively by Baumel.7 The present investigation was undertaken to determine which of the proposed mechanisms can be sub- A PAUL BOND IS Research Group Leader, Climax Molybdenum Co of Michigan, Ann Arbor, Mich. stantiated with experimental data obtained on ferritic stainless steels. High-purity 17 pct Cr alloys containing small controlled additions of carbon or nitrogen were therefore prepared, and then examined electro-chemically and metallographically. EXPERIMENTAL PROCEDURES Materials. Two series of experimental alloys were prepared from electrolytic iron and low-carbon ferro-chromium using the split-heat technique. In this technique, the base composition is melted, and part of the melt is poured off to produce an ingot. To the balance of the melt, the required addition is made and the next ingot cast. This process is repeated until a series of the desired compositions is cast. By this procedure the impurity levels are essentially constant within each series. All the alloys in the carbon-containing series were melted and cast in vacuum. The base composition in the nitrogen series was melted and cast in vacuum; subsequent ingots in the series were melted with additions of high-nitrogen ferrochromium, and cast under argon at a pressure of 0.5 atmosphere. Two additional alloys were produced starting with normal purity materials. They were induction-melted while protected by an argon blanket and cast in air. Table I gives the composition of the alloys. The 2-in.-diam ingots produced were hot-forged and hot-rolled to a thickness of 0.3 in. and then cold-rolled to 0.15 in. All specimens were annealed at 1450°F for 1 hr. The indicated sensitizing heat treat-s s ments were performed on annealed material. All heat treatments were followed by a water quench. Specimen Preparation. For the 65 pct nitric acid test, 1 by 2 by 0.14-in. specimens were wet-surface ground to remove surface irregularities and polished through 3/0 dry metallographic paper. For the modified Strauss test, $ by 3 by 0.14-in. specinlens were similarly prepared. Immediately prior to testing, the Table I. Compositions of the Alloys Composition, pct Alloy Cr hio C N 270A 16.76 0.0021 0.0095 270B 16.74 0.0025 0.022 270C 16.87 0.0031 0.032 270D 16.71 0.0044 0.057 271A 16.81 0.012 0.0089 27 IB 16.76 0.018 0.0089 271C 16.69 0.027 0.0085 271D 16.81 0.061 0.0O71 4073' 18.45 1.97 0.034 0.045 4075† 18.5 2.0 0.03 0.03

Jan 1, 1970

By Arthur F. Taggart

The following conclusions on the work of the Hardinge mill are based on data furnished to the writer by the Hardinge Conical Mill Co. in the form of the mesh cards hereto appended. Energy units (E. U.) and relative mechanical efficiencies (R. M. E.) are computed by the "volume method" of Stadler.' Screen apertures used are the average apertures of testing screeps of the meshes given. i . Card 122. June 28, 1912. Vipond Porcupine Mines Co., Ltd., Schumacher, Ont., Canada. Ore from mill bin. Gangue, quartz and basalt. 4.5 ft. by 13 in. ball mill, Capacity, 48 tons per 24 hr. Charge, 4,000 lb. balls. Speed, 33 rev. per minute. Horsepower, 15 to 17. Water, 100 per cent. by weight. (50 per cent. ?) Product deslimed and oversise reground in pebble mill, see Card 113. Feed to mill through 2-in. mesh. Mesh Feed, Per Cent. Discharge, Per Cent.. + 1in. 5.50 ....... + 3/4. 28.00 + in. 30.00 ...... + 1/4in. 19.72 ....... + 10 10.87 2.10 + 20 2.42 8.00 -20 3.51 .....,. + 40 ....... 22.68 + 60 ...___ 10.50 4-80 ....... 11.80 + 100 ....... 3.90 -100 ....... 40.15

Jan 1, 1916

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

By Donald L. Katz

THE Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July 1, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produces 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand' indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplification and generalizations are necessary to give the over-all picture in so short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, r, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City. Wilcox Secondary Recovery Association on Sept. 5;.1940. Some information is taken from a report to the Association by C. V. Sidwell on March 1, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." HISTORY OF WILCOX ZONE The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. 12.1 .4 and areal map of Fig. 2. The sand is of Ordivician age and is composed of well assorted, rounded' sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 was dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1937 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1941

[Executive J. V. W. REYNDERS, Chairman WILLIAM H. BASSETT E. DEGOLYER I-I. C. BELLINGER RICHARD PETERS, JR. Finance GEORGE OTIS SMITH, Chairman H. A. GUESS F. JULIUS FOHS Admissions GEORGE D. BARRON, Chairman DAVID LEVINGER P. A. MOSMAN H. K. MASTERS J. A, SINGMASTER Alternates F. G. BREYER C. W. HAMILTON F. E. PIERCE]

Jan 1, 1928

By E. J. Roberts

Hydrometallurgical operations and many processes in the chemical industry require the separation of dissolved material from solids. One of the decisions which has to be made in designing a plant for such an operation is how this separation shall be accomplished. It is the purpose of this paper to set forth the general principles involved in such separations in order that the optimum flowsheet and equipment may be selected. Countercurrent Decantation with thickeners, or C.C.D. as it is generally known, is, of course, only one way of separating dissolved material from undis-solved. Other unit operations such as Countercurrent Filtration (C.C.F.) and Countercurrent Classification (C.C.C.) are widely used. The same principles may also be applied to centrifugally assisted decantation, as with nozzle or solid bowl type centrifugals, and to separations using screens, either gravity or centrifugal type. Another form of countercurrent washing applicable to granular materials is practiced in continuous ion exchange operations. All of these operations depend on two basic principles, or combinations of these principles. In C.C.D. type operations the solids are concentrated into the smallest possible volume of liquor in each step and the resulting pulp then mixed with a more dilute liquor and recon cen trated, the liquors separated from the more dilute stages being advanced to dilute the more concentrated liquor in a previous solids concentrate, as is shown in Fig. I. This will be termed the solids concentration-solution dilution principle, or, for short, solution dilution. countercurrent decantation- type circuits. The second principle used in washing solubles from solids is that of solids concentration-solution displacement. Here the solids are restrained from movement while wash solution is forced through the interstices in a counter-current fashion, as in Fig. 2. In the simplest application of this principle, once the "cake" has been formed, it is not disturbed until the operation is completed. In continuous filters, the cake is merely moved under the successive washes and the displaced filtrates removed as in Fig. 4. Often, however, after one or two displacement washes, a repulping step is introduced, the cake reformed and washed again. This procedure brings the solution dilution principle into play as well as the solution displacement principle. Merely thickening ahead of filtration, which is often operationally advantageous, does not hybridize he circuit. It still can be a pure solution displacement operation from the washing

Jan 1, 1961

THE award from the fund established by Mrs. John-son, in memory of her husband, J. E. Johnson, Jr., to be given to some promising engineer, not over 40 years of age, because of meritorious research, inven-tion or contribution to the professional literature of iron and steel along the lines of blast-furnace process, has been given, for, 1928, to P. H: Royster. Mr. Royster was born at Raleigh, N. C., in 1888. and graduated from the University of North Carolina, in 1907, taking his A.M. degree at, the same school in 1908. He then went to Harvard where he continued research work in physics. After engaging for a while in commercial research in the turbine department of the General Elec-tric Co. and with Cutting and Washington he joined the staff of the Bureau of. Mines in 1916 and was assigned to work on the physical chemistry of the blast-furnace process. He worked with A. L. Feild on slag viscosity and they jointly presented-to the Institute the. papers on "Temperature and Viscosity Relations in the Ter-nary System CaO-A12O3-SiO2" (TRANS. LVIII, 658) and "Slag Viscosity Tables for Blast-furnace Work" (TRANS. LVIII, 650). He also presented a paper on "Production of Ferromanganese in the Blast 'Furnace" .(TRANS. LXII, 18), and jointly with T. L. Joseph contributed a paper on "Effect of Coke Combustibility on Stock Descent in Blast Furnaces" (TRANS. LXX, 236), and another on "Pyrometry in Blast-furnace Work" which was included in the special pyrometry volume published in 1920. The titles of these works perhaps sufficiently indicate the part Mr. Royster has played in the notable research work on the blast-furnace process carried on by the Bureau of Mines, and for which the committee recommended him to the Board of Directors to receive the Johnson award.

Jan 2, 1928

By Henri S. Swolfs

INTRODUCTION In this paper we present preliminary results of a research program in site characterization methodology. We are interested in under- standing the response of discontinuous rock to mechanical, hydrologic, and thermal loadings. To carry out such a study we selected a field site with simple geology, uniform distribution of lithologies, and easily verifiable boundary conditions on temperature, fluid flow and stresses. The spatial distribution of fractures at the site was established and tests were conducted to determine the temperature field, hydrology, rock-mass properties, and in situ stresses. As part of the study selected borehole instruments were compared to assess their performance and reliability. SITE GEOLOGY The study area is in the eastern part of South Table Mountain, a mesa near Golden, Colo. The exposed cap rock is a single lava flow of uniform thickness (6-7 m) that rests on the clastic sediments of the Denver Formation (Van Horn, 1976). The surface of the cap rock (N. 75º E., 3º S.) is topographically featureless and slopes south- southeast; drainage is predominantly downdip and punctuated by occasional contact springs. The age of the lava flow is 64-65 m.y., or early Paleocene. Paleo- botanic evidence confirms the upper part of the Denver Formation as Paleocene (Van Horn, 1976). "Rapid-rock" analyses of core samples from the lava flow at three depths (0.2, 3.3, and 5.8 m) suggest a uniform chemical composition throughout with an increase in the Fe2O3/ FeO ratio (1.05 to 1.60) with increasing depth, reflecting the existence of a perched water table in the lava flow, To identify the rock

Jan 1, 1984

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By Ralph Sweetser

THE Round Table. on Qualities of Pig Iron, under the auspices of the Joint Committee on Qualities of Pig Iron, which is made up of members of the American Institute of Mining and Metallurgical Engineers, the American Foundrymen's Association, the American Society for Testing Materials, the Gray Iron Institute, and the. Malleable Iron Institute, was held at the Palmer House, Chicago, Ill., on Oct. 1, 1935. PROCEEDINGS R. H. SWEETSER,* New York, N. Y.-Seven years ago last June we had a round table on qualities of pig iron1, and at that time the foundrymen were out with their battle-axes for the blast-furnace men, and the open-hearth men were doing the same thing. After that meeting there was really a determined effort to find out about the qualities of pig iron, and great progress has been made all along the line. This afternoon we want to have a frank discussion of the qualities of pig iron, whether it is the molten pig iron going into the steel plant, or cold pigs going to the different foundries. We ought to hear something from Dr. J. T. MacKenzie, who is chairman of the Joint Committee, and from Mr. R. E. Kennedy, the tech-nical secretary. J. T. MACKENZIE, t Birmingham, Ala.-As a result of that meeting in Chicago, there was considerable agitation in the Foundrymen's Association to develop a set of tests for pig iron. One of the difficulties was that nobody talked the same language on shrinkage, draws, live iron, dead iron, and so forth, which were the main com-plaints against pig iron. By request of a committee of the Foundrymen's Association, the Bureau of Standards ran a comprehensive set of tests that did develop the prin-ciples governing the optical pyrometer as applied to cast iron and pig iron. Then the Bureau went on further with the fluidity test, and developed a method for the absolute changes of volume at the freezing point.

Jan 1, 1936

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By R. Lagneborg

WhEN mechanical twins initiate cracking it has been proposed1 that the friction stress for dislocation motion, in the Cottrell criterion for brittle fracture2 should be replaced by the stress required to propagate a twin, ttp. TF is the fracture stress, d the grain diameter, ß a geometric constant, u shear modulus, and y the effective surface energy. Since TTp is likely to vary with grain size, it cannot be substituted by a constant in Eq. [I]. If an expression for the energy change caused by a twin in a stressed material could be obtained, it is in principle possible to compute the critical size of the twin, i.e., the size at which the system can decrease its energy spontaneously, as a function of applied stress, thus giving the stress required to just barely propagate the twin, i.e., TTP. Consider a circular twin disc with a radius r and having a lenticular cross section, Fig. 1. Twin dislocations3 of strength b exist in the twin boundary parallel to the twin plane, one loop on each atomic plane. Assume that the total numbers of loops, n, can be replaced by one circular loop of a multiple dislocation, nb with a radius r. The energy change of the system, AW, due to such a twin in an applied stress field can then be calculated: The first term is the total twin surface energy, the second the elastic energy due to the twin dislocations, and the third the energy released by the twin in the applied stress field. yt is the twin boundary energy, r, the radius of the dislocation core, and T the applied

Jan 1, 1968

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983

By John Chipman, Carl F. Floe

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By C. Graeme-Barber, R. L. Bell, T. G. Langdon

An analysis is made of the formulas and ,methods used to estimate the contribution of grain boundary sliding to the overall strain of a polycrystal. The errors involved in the approximations and/or ,mistakes in earlier work are assessed quantitatively so as to make possible the critical use of previously published data. SINCE it has been found that, under conditions of very slow creep, the strain due to grain boundary sliding (?gb) may contribute as much as 80 pct of the total creep strain,1,2 it is obviously important to have reliable methods for estimating this grain boundary strain. In two recent papers Stevens3,4 has drawn attention to the pitfalls encountered in assessing ?gb. He criticizes 1) the assumptions made in the derivation of some of the formulas for ?gb, and 2) the indiscriminate averaging procedures used for obtaining the quantities substituted in these formulas. These and further criticisms of earlier work are mostly valid. Unfortunately the only formulas and procedures recommended are either impossible or very difficult to apply in practice. Furthermore no attempt is made to assess the errors involved by the earlier approximations or mistakes, and so it is not possible to make critical use of any of these early dab. The present article attempts to improve on these shortcomings by reference to empirical verification of easily applied formulas whose theoretical derivations involve some otherwise unjustifiable assumptions, and by a quantitative assessment of the errors in previous work. DEFINITIONS First it is necessary to define the terms and symbols to be used. The choice of symbols preferred here is a logical combination and extension of the v introduced by McLean5 and the u by Brunner and rant.' In Fig. 1 the two grains X and Y are displaced by the sliding vector AC. u is the component of sliding resolved along the stress axis, v is that measured perpendicular both to the stress axis and to the specimen surface, and w is that measured perpendicular to the stress axis but in the plane of the surface. Two angles define the orientation of the grain boundary: 8, between the stress axis and the surface trace of the boundary, and +, the internal angle on a longitudinal section cut perpendicular to the surface. In computing the strain resulting from the boundary displacement at all the in- dividual boundaries in a polycrystal the components u, v, or w are sometimes averaged along a longitudinal line (i.e., parallel to the stress axis), sometimes along a transverse line, and sometimes at randomly chosen boundaries. Averages obtained in these three ways are given subscripts 1, t, and r, respectively. Stevens rightly calls attention to the possibility of non-equiaxed grain shapes either at the start or at the end of deformation. In this article all values of numbers of grains per unit length will refer to measurements made before deformation. The subscripts 1 and t will be used for the number of grains per unit length obtained along longitudinal and transverse lines, r for that obtained by averaging along a number of randomly directed lines. FORMULAS FOR ?gb ?gt, as a Function of u. An obvious truth is that cgb can, in principle, be obtained by summation of all the v components at the boundaries intersected by a longitudinal line of known length I, viz.: where nl is the number of grains per unit length, parallel to the stress axis, in the unstrained specimen. There are assumptions in the analytic derivation of Eq. [I] due to Brunner and rant' but ~achinger' arrived at Eq. [la] by a rigorous method. Unfortunately the experimental procedure required by Eq. [ la] proves very difficult as boundary migration tends to obscure the points at which the longitudinal line meets the grain boundary and the errors on such measurements tend to be large, see Fig. 2. For example, on a specimen of Magnox AL 80 at a creep strain of 9.7 pct, 300 measurements of u obtained from the points of intersection of a longitudinal line with the grain boundaries gave ul = 8.95 ± 3.58 pm, or an error of ±40 pct, at the 95 pct confidence limit. These large errors due to migration may be avoided by measuring u from the separation of the segments

Jan 1, 1968