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By D. J. McAdam, G. W. Geil, R. W. Mebs

As shown in previous papers by the authorsg-17t the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses. A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number Of possible com-binations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers,'-'' the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the three of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals ''should,, behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or ,plasticdeformation, fracture,, and a "brittle frat-ture.H In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture' In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1948

By R. W. Mebs, G. W. Geil, D. J. McAdam

As shown in previous papers by the authorsg-17t the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses. A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number Of possible com-binations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers,'-'' the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the three of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals ''should,, behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or ,plasticdeformation, fracture,, and a "brittle frat-ture.H In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture' In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1948

By Paul L. Cloke, S. R. Titley

Paul L. Cloke (Assistant Professor, Dept. of Geology and Mineralogy, The University of Michigan, Ann Arbor, Mich.) - On examination of the paper by S. R. Titley it appears that several errors have been made, many of them of a fundamental nature. It is the intent of this discussion to point out these mistakes, and, insofar as possible with the data at hand, to correct them. EXPERIMENTAL WORK Ferrimolybdite-Limonite-Water: The results of the experiments described are very difficult to interpret; nevertheless, a correct interpretation is essential as is pointed out subsequently. The difficulties become apparent when reasons are sought for the continuing change of pH after conversion of ferrimolybdite to ferric hydroxide and for the change of pH when -stirring is stopped after a steady value has been reached. In seeking an explanation of this experiment it seemed to this writer that the (temporarily) steady pH values might be due to kinetic rather than equilibrium effects. In this view the steady pH on stirring might be explained as a balance of several reactions proceeding simultaneously. The first of these would be the slow solution of ferrimolybdite,

Jan 1, 1964

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period Feb. 10, 1916 to Mar. 10, 1916: D. A. S. Bell, Ottawa, Can. E. B. Latham, Santa Maria, Cal.. John Cooper, Exeter, Devonshire, Eng. H. N. Lawrie, Portland, Ore. I. Dally, Seattle, `Wash. L. A. Levensaler, Tacoma, Wash. George W. Evans, Seattle, Wash. George J. Lyon, Schenectady N. Y. Alexander Fyfe, London, Eng. Fred MacCoy, Antofagasta, Chile. F. C. Greene, Seattle, «rash. J. Mitchell-Roberts, London, Eng. I. Ishikawa, Tokio, Japan. Chas. W. A. Sultan, Yonkers, N. Y. William Kelly, Vulcan, Mich. R. B. Tinsley, Big Stone Gap, Va. Paul S. King, Wilmington, Del. Walter E. Trent, Reno Nev. Oscar Lachmund, Greenwood, B. C. Alfred W. G. Wilson, Ottawa, Can. J. S. Lane, New York City. Nelson Dickerman has resigned as general Manager of the Pato Mines (Colombia), Ltd., and The Nechi Mines (Colombia), Ltd., and will return from Colombia to San Francisco, Cal., the latter part of April. W. A. Prichard has been appointed as his successor.

Jan 4, 1916

By George F. Weaton, Carleton C. Long, H. I. Najarian

Partial descriptions of the operation of the St. Joseph Lead Company's Joseph-town smelter have been published. In, 1936 the electrothermic production of zinc oxide was described;' in 1939 appeared a description2 of the electrothermic method of producing zinc metal. Inasmuch as the plant capacity has more than doubled, and in view of the fact that operating practices have improved greatly since these publications, it seems worth while to prepare a fresh description of the present-day elec-trothermic zinc plant and practice. Josephtown smelter is situated on the south side of the Ohio River about 3 miles below its confluence with the Beaver River. In addition to river barge, the smelter is served by Pennsylvania state highway No. 18 and by a spur line of the Pittsburgh and Lake Erie Railroad (N.Y.C.). A recent extension of this spur line connects with the Pennsylvania Railroad. As originally contemplated the plant was to handle only the product of the com-pany's own mines in St. Lawrence County, New york, but owing to the incessant demand for zinc and zinc oxide, it has been necessary to supplement New York concentrates with foreign ores (principally from Quebcc and the Argentine). The general operational procedure followed comprises roasting the sulphide con-centrates, converting the sulphur dioxide into sulphuric acid, preparation of a strong-structure sinter from the calcine, crushing &lid sizing of coke, reduction of coke-sinter mixture by electrothermic means, condensation of the evolved zinc vapor to make zinc metal or burning of the zinc vapor to make zinc oxide, collection and packing of the zinc oxide. Dusts recovered by the roaster and sinter Cottrells are treated in the leach plant for separation of lead sulphate, cadmium metal and zinc sulphate. The general flowsheet is shown in Fig. I. Principal Items OF Equipment Roaster Plant Concentrate drier, 6-ft. 'ia. by 4O ft. 5 in., countercurrent, direct gas-fired. 3500-~on concentrate storage in three vertical steel tanks. Five modified Nichols-Herreshoff twelve-hearth roasters, 21 ft. 6 in. in diameter. Four fans for shaft-cooling air. One threedrum Stirling water-tube waste-heat boiler, 4'8 hp., 200 1b. Per sq. in., with connections to upper and lower balloon flues. Direct gas-fired countercurrent rotary-kiln roaster for Cottrell dust. Necessary conveying equipment, described below. Instrumentation consists of: draft indicators, (3d hearth); various manometers; pyrometer served by thermocouples in each hearth, entrance and exit of waste-heat Joseph. entrance and exit of each hot Cottrell; roaster draft recorder and shaft air-pressure controller; temperature recorder and controller (10th and 12th hearths); SO* recorder (waste-heat boiler n

Jan 1, 1944

By Walter O. Roberts

A TOTAL eclipse of the sun is a brief, exciting spectacle witnessed by most men but once or twice during a lifetime. But to an astronomer an eclipse of the sun is an event of utmost scientific importance. For then, certain phenomena of the sun normally obscured by the brilliant glare of sunlight become spectacularly visible. For over seventy years prior to 1930 astronomers vainly attempted to discover a means of observing all of these eclipse features of the sun without a natural eclipse. But in 1930, through the genius of the French scientist, Bernard Lyot, astronomers met final success. Dr. Lyot invented a new kind of telescope known as a coronagraph, which made possible photography of all of the eclipse features of the sun. In 1940 Harvard University completed final testing of its Lyot-type coronagraph. the only one in the Western Hemisphere, and shipped it to Climax, where Donald H. Menzel, of Harvard College Observatory, supervised its establishment on the southeastern edge of the mining community of the Climax Molybdenum Co., with whose help and advice the modern residence and telescope dome of the observatory were constructed. Ever since that summer the station has been operated by me, first as a graduate student, and now as a staff member of Harvard College Observatory.

Jan 1, 1946

By John D. Sullivan

Leaching of copper ores is a comparatively old art, probably dating back to medieval times. The leaching of mixed oxidized-sulfide ores, however, is modern. The first modern plant leaching mixed ores was at Ajo, Ariz., where commercial operations commenced in 1917. While the ore at Ajo was primarily oxidized there was always some sulfide present. The Inspiration leaching plant, which was put in operation in 1926, may be considered the first plant constructed for the extraction of both sulfide and oxidized copper. The pioneers in leaching mixed ores had a difficult task before them since they had very little fundamental data on the chemical and physical factors of leaching. For the very large amount of painstaking experimental work that was done before building the Ajo and Inspiration leaching plants the reader is referred to the original articles.' For a period of several years the writer worked on problems connected with the chemistry and physics of leaching mixed oxidized-sulfide ores. This paper summarizes the experimental work and discusses various factors involved in leaching ores. It also presents many data heretofore unpublished. Among the new data are those on chrysocolla, pages 518 to 519, inclusive; dioptase, page 519; covellite, page 529; virtually all those on chalcopyrite, pages 531 to 533, inclusive; enargite, page 533; and tetrahedrite and tennantite, pages 534 and 533. The oxidized copper minerals of commercial importance in American ores are azurite, Cu3(OH)2(CO3)2; malachite, Cu2(OH)2CO3; chrysocolla, CuSi03.2H2O; tenorite (or melaconite), CuO; and cuprite, Cu2O. Dioptase, CuSiO3.H2O is less common. Brochantite, CuSO4.3Cu(OH)2, while the chief mineral in the ore at Chuquicamata, is not of major importance in the United States. Metallic copper, while chemically not so, is frequently classed as an oxidized mineral of copper. The most important sulfide minerals are chalcocite, Cu2s; covellite, CuS; bornite, Cu5FeS4; and chalcopyrite, CuFeS2. Less important complex sulfides are enargite,

Jan 1, 1934

On. Tuesday, Apr. 8, the Rocky Mountain Club held its 12th annual dinner at the Waldorf-Astoria, New York. In reporting the dinner the Evening Telegram says: "General Coleman du Pont was sort of master of ceremonies, and he conducted the affair at the end of a Colt .45. It was the General's `forty-five' which filled the banquet hall of the Waldorf-Astoria with the brand of smoke which Uncle Sam showered so generously upon Germany's hordes. It was General du Pont's `forty-five' which bellowed and thundered and echoed through Fifth avenue, scaring horses and shell shocking pedestrians: But no one was hurt or badly shocked except those who could not discern the artistry of Miss Doraldino's dance. "There were Western men around the table who have just come hack from over there. For instance, there were Brigadier General G. H. McManus, General Shanks and a score of others. And there were Thomas H. Watkins, who is said to own half the State of Pennsylvania and is known as the `Coal Baron'-of Pennsylvania,, and Alba B. Johnson, president of the Baldwin Locomotive Works, each one a Westerner, with personality and type suggestive of some of the wonderful men Bret Harte wrote so much about. "It seemed as though General du Pont, who was chairman of the Reception Committee, tried to eclipse all former meetings, and he succeeded if congratulations are a criterion. " General du Pont startled the management of the Waldorf and surprised the diners by staging a three-round bout between Frankie Fay and Phil Wagner. The clash between these two featherweights made Waldorf history, because it was the first boxing contest ever held in the hotel. Tex Rickard, who is going to chaperone Jess Willard and Jack Dempsey in a fight in the near future,-was scheduled to referee the contest, but at the last moment, for some obvious reason, M. E. Schermerhorn was sent in as third man. The bout was a slashing one. Miss Amparito Farrar, lately returned from France, where-she sang for the 'dough-boys;' Eleanore Wetmore, the Rath Brothers and Phil Baker were among the others who entertained.

Jan 5, 1919

By J. T. Hayward

Studies of the forces and conditions governing the recovery of petroleum from natural reservoirs indicate that a low gas-oil ratio increases ultimate recovery, retards the encroachment of water and tends to reduce lifting costs. Methods for controlling and reducing gas-oil ratios in producing wells consequently have been given considerable attention during the past few years. However, during this same period, the production from wells in nearly all fields has been fixed by proration agreements and it is the opinion of the writer that where a well is required to produce steadily at a predetermined rate, less than its "potential" or maximum capacity, the gas-oil ratio will depend only upon the rate of production, and will be independent of the method of production and of the design of equipment in the well. If no change in the rate of production is contemplated, efforts directed to improving the gas-oil ratio by altering the diameter of the flow string, changing the position of the choke, assisting the flow with gas-lift or pump, etc., will be unsuccessful. This viewpoint is not new. It was presented by H. N. Marsh and B. H. Robinson in 1929,' but it has not been generally accepted. Although engineers believe that the rate of withdrawal and not the equip ment used governs the water-oil ratio, a similar opinion regarding the gas-oil ratio is not so commonly admitted. The rates of flow of oil and gas into the base of an oil well depend upon the following conditions: 1. The characterist-ics of the oil and gas. 2. The characteristics of the underground reservoir. 3. Temperature and pressure conditions in the reservoir. 4. The back-pressure held against the face of the sand. In operating a well, the only one of these conditions over which control may be exercised through operating procedure and the use of equipment above the sand is the back-pressure at the face of the sand. Strictly speaking, the back-pressure varies over the face of the sand, owing

Jan 1, 1932

ALABAMA Aldrich.-Lloyd, T. W. Anniston.-Carrington, F. G. Klugh, B. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson V. Salmon, h. S. Stuart, Q. W. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Armstrong. W. D. Ball, E. M. Bonnyman, J. Bush, M. W. Carter, E. Crawford, G. G. Davis, C. B. Dryer. T. B.

Jan 1, 1923

• As part of $850,000 granted by the House Appropriations Committee for development of manganese in the U.S., the Bureau of Mines will build a pilot plant at Artillery Peak, Ariz., for development of low grade manganese ores. • The historic Argo tunnel and mill in Idaho Springs, Colo., will reopen shortly for the mining of uranium. The Uranium Co. of America has acquired control of the tunnel and mill and 12 nearby mining properties. J. H. Rodgers and G. C. Ridland will manage the operation. •The opening of a new 4000-ton per day coal mine in Washington Co., Pa., and the reopening of another mine of the same capacity in Fayette Co. has been announced by the H. C. Frick Coke Co. They'll help meet added war demands. •A 7000 bbl per day commercial synthetic liquid fuel plant, making gasoline from natural gas at Brownsville, Texas is being operated by the Carthage Hydro-col Corp., a Texaco subsidiary. The gasoline is produced by the Hydrocol process, chemically similar to the Fischer Tropsch process, but differing mechanically in several ways. To operate the process it has been necessary to build an oxygen plant producing 95 pct pure oxygen in quantities equal to U. S. production of commercial oxygen in 1946. •Over 96 pct of the class of 1950 at Montana School of Mines are now employed,, in industry, and they're scattered from MIT to the island of Cuba., • Cobalt, heretofore almost entirely imported, will soon be produced in Idaho. The Calera Mining Co. is building a 600-ton mill in which a cobalt and copper concentrate will be obtained from Idaho ores. •Plans for mining iron ore on the Conarky Peninsula in French Guinea, (an ECA project) call for equipment purchases as follows: 8 wagon drills, electric shovel for mining, conveyor for the port, 8 trucks, wrecker, 2 tractors, as well as miscellaneous accessories and spare parts. •A low-grade lead-zinc mineralization, located east of any known ore bodies in Utah's East Tintic district, has been located by a 2000-ft wildcat USGS drill hole. * Higher-than-going rates have been authorized by the Munitions Board for its stockpile program, where domestic production of scarce materials is low or uneconomical. Payment in excess of 25 pct over the foreign price is now permitted. •A new self-centering conveyor roll, developed by Carnegie-Illinois Steel, is expected to revolutionize materials handling. It completely eliminates the necessity for sideguides to keep materials on a conveyor. See P. 1028. •Great Britain's socialized coal industry employs twice as many miners, but produces less than half as much coal as America's coal industry. last year, British mines produced 28 million fewer tons of coal than the output of the same ,mines in 1939. Absenteeism amounted to a big 12 pot of working time. • Labor market conditions have tightened on almost a country-wide scale. Only 4 out of 143 major labor market areas have a substantial surplus -- less than half the total for May. Growing scarcities of skilled labor are in evidence.

Jan 10, 1950

By Leroy Gardner

EVERY reader of this paper is well aware of the fact that the prolonged inhalation of large amounts of free silica dust results in fibrosis of the lungs, and that other inorganic dusts, except those of asbestos and the mineral poisons, are thought to be relatively harmless. But probably few have had opportunity to visualize the effects of silica, asbestos and other minerals upon living tissues. The ideal demonstration would be based upon sections of lungs from human beings that had inhaled com-parable concentrations of different dusts for a unit period of time. Such material is generally difficult to obtain and in some instances is of ques-tionable value because the subject has been exposed to more than one kind of dust. A demonstration could be prepared from the lungs of animals. However, so many months or even years are required to com-plete the exposure to each kind of dust that enough material has not been accumulated. For a general survey of the action of different types of dust, I am therefore compelled to use the tissues of animals that have been injected with suspensions of dust particles. The injection method offers certain advantages. The quantity, the particle size and the state of dispersion can be controlled with sufficient accuracy so that the tissue responses to different minerals can be accu-rately compared. The method insures contact between the tissues and the mineral particles; protective mechanisms, which may prevent the inhalation of certain types of foreign body, never come into play. If the pathway of injection be one that minimizes nonspecific injury, the tissue responses may simulate those produced by inhalation but they develop somewhat more rapidly. It should always be remembered that injection methods merely demonstrate the capacity of various kinds of minerals to provoke reaction in the tissues; whether the same substances are inhaled from atmospheric suspension and accumulate in the lungs in dangerous quantities can be demonstrated only by inhalation.

Jan 1, 1938

T. S. FULLER, Chairman C. H. MATHEWSON, Past-chairman W. A. SCHEUCH, Vice-chairman J. L. CHRISTIE, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer Executive Committee H. A. BEDWORTH W. M. PEIRCE D. K. CRAMPTON A. J. PHILLIPS E. H. Dix JR. GUY C. RIDDELL R. F. MEHL J. WALTER SCOTT JEROME STRAUSS Finance Committee C. H. MATHEWSON, Chairman W. M. CORSE H. S. RAWDON ZAY JEFFRIES SAM TOUR Data Sheet Committee R. S. ARCHER Chairman N. B. PILLING Vice-chairman L. W. KEMPF JEROME STRAUSS A. J. PHILLIPS F. L. WOLF'

Jan 1, 1932

By C. L. Burrill

The forecasts presented in this paper constitute an attempt by the writer to predict the pattern of the consumption of petroleum products in the United States during the period of transition from war to peace. Although, in preparing the estimates, secular trends were not overlooked, greater emphasis was placed upon considerations of a cyclical character, or upon influences which might be peculiar to parts of the period. The estimates do not extend beyond the year 1950 because by then conditions in the industry should have returned to normal. The consumption of petroleum products is affected, of course, by changes in the condition of business in general. Before estimates of petroleum consumption could be prepared, therefore, it was necessary to predict the pattern of general business during the period under review, particularly the economic series that in the past have shown the closest relationships with petroleum consumption. It is the writer's view that business activity in this country (as measured by industrial production) will be higher on the average during the period between the end of the war and the year 1950 than it ever was before during a peacetime period of the same duration. When the war is over, consumers will have saved amounts of money that will be very large as compared with any previous accumulations. There is little question, therefore, as to the financial ability of consumers to purchase goods. The production of many durable consumers' goods, such as automobiles, refrigerators and radios, has been completely stopped since early in the war; also, many semidurable and nondurable consumers' goods have not been available in the quantities or the qualities desired. There is considerable needi therefore, for consumers to purchase goods after the war. The important question is whether consumers will purchase goods in "1arge enough quantities to keep our economy running at a high level. The writer answers this question in the affirmative. The mere existence of very large consumer savings lends considerable support to this view because, with such backlogs of " security," consumers can afford to spend more of their current earnings than they otherwise could. Also, several polls have been taken, which indicate that consumers expect to buy large quantities of a variety of goods. Some of the savings, therefore, probably will go into current consumption. Even though this percentage is relatively small, so that the bulk of the funds accumulated by consumers during the war continues to remain as savings during the period under review, spending should be great enough to start the production cycle and keep it

Jan 1, 1945

George B. CoRless, Chairman. Superintendent, Gulf Coast Division, Humble Oil & Refining Co., Houston, Texas. W. H. Geis, Associate Chairman. Geologist, Los Angeles, California. Benjamin C. Craft, Secretary-Treasurer. Associate Professor, Petroleum Enginecring, Louisiana State University, Baton Rouge, La. Executire Committee George B. Corless, Chairman. M. Albertson, Production Engineer, Shell Petroleum Corporation, Houston, Texas. D. R. Knowlton, General Production Superintendent, Phillips Petroleum Co., Bartlesville, Oklahoma. R. P. McLaughlin, General Manager, Dominguez Oil Fields Co., Los Angeles, California. Hallan N. Marsh, Production Engineer, General Petroleum Corporation of California, Los Angeles, California. Theron Wasson, Chief Geologist, The Pure Oil Co., Chicago, Illinois. Production Engineering M. L. Haider, Vice-chairman. Petroleum Engineer, Carter Oil Co., Tulsa, Oklahoma. Joseph Chalmers, DeBataafsche Pet. Maatschappij, The Hague, Netherlands. Emile HugUenin, Deputy State Oil and Gas Supervisor, Los Angeles, California. Carl E. Reistle, Jr., Petroleum Engineering Department, Humble Oil & Refining Co., Houston, Texas. Production J. TERry Duce, Vice-chairman. Geologist, The Texas Company, New York, N. Y. Basil B. Zavoico, Associate Vice-chairman. Geologist, The Chase National Bank, New York, N. Y. Engineering Research R. L. Huntington, Vice-chairman. Associate Professor, Petroleum Engineering, University of Oklahoma, Norman, Oklahoma. Economics Sidney A. SwensrUd, Vice-chairman. Assistant to the President, Standard Oil Co. (Ohio), Cleveland, Ohio. Refinery Engineering Walter Miller, Vice-chairman. Vice-president, Continental Oil Co., Ponca City, Oklahoma. 10

Jan 1, 1938

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

ALABAMA. Aldrich, Aldrich, W. F. Anniston, Noble, A. E Bessemer, Abbott, C. E., Fer¬gusson, V. Birmingham, Aldrich, T. H., Jr., Bowron, C. E., Bowron, J., Collord, G. L, Crockard, F. H., Davis, F. H, Dimmick, F. D., Hillman, Ludwig, C. P., McCarthy, M. E., McCormack, G B., McCrery, Ramsay, E., Shook, A. M. Car¬bon Hill, Pill, J. R. Coal City, Lydecker, I. S. Gannts Quarry, Hiller, E. Helena, Squire, J. Holt, Shook, J. \V. Huntsmlle, Moss. Lehigh, Toulmin. Oxmoor, Green¬amyer, A. G. Rock Run, Garvin, J. M. Sheffield, Miller, D. I. Woodward, Lodge, J., Woodward, A. H. ALASKA. Ellannar, Stevens, B. Fairbanks, Hamilton, A. L, Robe, L S. Hadley, John¬son, P. Jualin, Hoggatt, W. B. Juneau, Denby, Thane, B. L., Whipple, J. R. Katalla, Hampton, W. H. Ketchihan, Barber, J. C., Geiger, A. \V., Parker, J. L. Niblack, Finck, W. N., Niedling, B. B. Nome, Garfield, C. D. Tin Oity, Fay, A. H. Treadwell City, Kinzie, Stow, H. P. Valdez, Esterly, G. M., Hazelet.

Jan 1, 1910

Truman H. Aldrich W. Lawrence Austin W. S. Ayres John Henry Banks Wrn de L Benedict Andrew A Blair Walter M. Brodie H. H. Burden Charles Butters

Jan 1, 1932

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

[Executive E. DEGOLYER, Chairman SYDNEY H. BALL WILLIAM H. Bassett RICHARD PETERS, JR. J. V. W. REYNDERS Finance GEORGE D. BARRON, Chairman H. A. GUESS GEORGE OTIS SMITH]

Jan 1, 1928