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By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

[Separates of all the Technical Publications published in 1929 are available at lnstitute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the Transactions.] Metal Mining Technical Pdbli- Title Author Meeting Trans. cation . Volume No. and Page* 182-A-23 The Royal Commission on Mining Henry Louis New York Subsidence Feb., 1929 183-A-24 Cycles in Metal Production D. F. Hewett Nen. York T29, 65, 95 Feb., 1929 199-A-25 Ventilation at the United Verde Oscar A. Glaeser New York T29,- 114. Mine Feb., 1929 206-A-26 Air Conditioning In Deep Mines R. W. Waterfill New York T29. 99, 112 Feb., 1929 245-A-27 Bumps in No. 2 Mine, Springhill, Walter Herd New York Nova Scotia (with discussion) Feb., 1929 257-A-28 Misfires: Their Causes, Prevention New York and Treatment on Occurrence Feb., 1929 Misfires in Anthracite Coa1 T. D. Thomas Mines (With Discussion) Misfires in Bituminous Coal W. H. Forbes Mines (With Discussion) Misfires in Non-metallic Mining A. W. Worthington (Limestone) (With Discussion) Milling and Concentration 195-B-15 A Study of Differential Flotation C. R. Ince New York Feb., 1929 196-B-16 Elements of Operation of the Arthur F. Taggart New York Pneumatic Table H. L. Lechmereoertel Feb., 1929 202-B-18 Silver-bearing Minerals of Some A; W. Habn New York T29, 325 Ores from Tintic Mining District Feb., 1929 204-B-17 Experiments with Flotation Re- A. F. Taggart New York agents T. C. Taylor Feb., 1929 C. R. Ince 208-B-20 Cyanide Regeneration or Recov- C. W. Lawr Sun Francisco ety as Practiced by the Com- Oct., 1929 pania Beneficiadora de Pachuca, Mexico 214-B-19 Calculations in Ore Dressing W. Luyken New York E. Bierbraer Feb., 1929 217-B-21 Differential Grinding Applied to Leon M. Banks San Francisco Tailing Retreatment George A. Johnson Oct., 1929 224-B-22 Reducing and Oxidizing Agents Research Staff San Francisco and Lime Consumption in Flo- of United Verde Oct., 1929 tation Pulp Copper Co. 247-B-23 Copper Sulfate as Flotation Acti- 0. C. Ralaton San Francisco vator for Sphalerite 0. R. King Oct., 1929 F. X. Tartaron

Jan 1, 1929

By W. L. Saunders

It has been estimated that the value of the mineral products of the United States is about $2,000,000,000 a year; that about $25,000,000 is expended annually for explosives and that about double this sum is paid in wages where blasting is done. The value of the mineral products does not adequately express the importance of the industry involved in the excavation of rock and ore because of the enormous sums of money expended in tunnel driving, in quarries, and in open-cut excavation generally. We know that the Catskill Aqueduct in the neighborhood of New York, which is now nearing completion, has cost some $165,000,000 and that about one-third of this may be rated as rock excavation. These illustrations are given in order to call attention to the great importance of an industry the extension and development of which in our industrial life depend so much upon the economics of rock drilling. Reference has been made to the new Catskill Aqueduct. There are three aqueducts leading into New York, each built at periods separated by some 20 years of time. The first one, known as the Old Aqueduct, conveys the waters of the Croton river to New York City in a manner which reminds one of the old Roman aqueducts, the ruins of which are still in evidence. The engineers who laid out these old conduits sought to direct their lines around the hills and into the valleys, at all times avoiding the rock. When it was necessary to cross a river or a deep ravine, a bridge or causeway was constructed. High Bridge, over the Harlem river, is an arched masonry viaduct differing in no essential features from the aqueducts of the Romans. When the second Croton Aqueduct was built, about the year 1890, the art of drilling rock had been so far perfected, and the use of explosives, through the invention of dynamite, had become so general, that this waterway was planned and executed on straight lines, following rather than avoiding the rock. The second Croton Aqueduct is a tunnel through rock, about 32 miles in length; material gneiss, almost as hard as granite. Its construction was made practicable by sinking

Jan 1, 1914

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By William J. Douglas, Jack T. Urie, Randall D. Metz

Production and financial planning for a new underground mine requires the coordination of equipment and coal reserves in a manner which assures that resources are utilized efficiently in achieving the target mine production. It is necessary to establish the productions which are attainable at the section level during different mining operations (advance, retreat, development) and under different mining conditions (roof, seam height, resource quality). It is also necessary to identify the interactions between production plans and ventilation equipment So that operations can be carried out without disruptions caused by inadequate ventilation. A set of computer models has been applied in planning a number of new coal, oil shale, and phosphate mines. A critical path production model, CPMINE, was used to determine face production levels for different cut sequences and seam heights, taking into account machine performance characteristics and operational availabilities under these varying conditions. The results formed a production data base for use in the mine sequencing model, MPLAN. This model processes each of the segments of a user-defined mine sequence network (strategy tree) taking into account the equipment available for mining operations and the previously determined production scheme devised by the mining engineer. Mine ventilation was analyzed with an expanded version of the Penn State MVS Ventilation model to determine fan and ventilation shaft requirements for supporting alternative production strategies. The MCOM mine cost analysis model has been applied to evaluate the economic performance of mining alternatives. The results of these studies were used to make decisions relating to equipment selection and acquisition schedules for both room-and-pillar and longwall mining systems. The approach and procedures which were used during these studies are described.

Jan 1, 1983

By F. W. Clark

At the present time, when lixiviation versus amalgamation is being so thoroughly discussed by practical men, and published information is so meagre, the following tests, made by students in the mining laboratory of the Massachusetts Institute of Technology, may be of interest to others. The ore experimented upon was obtained from the Sombrerete mines near Zacatecas, Mexico. A careful analysis of the dried sample resulted as follows : Per cent. SiO2,............62.79 S.............13.86 Al2O3............4.39 Fe,............11.26 Zn,............1.57 CaO.............2.91 MgO,........... 0.06 Cu,.............0.12 Pb,.............0.40 Sb and As,..........trace CO2,............2.35 Ag,.............0.16 99.87

Jan 1, 1886

By E. A. Anderson

In 1918 the American Society for Testing Materials held a symposium2 on what was then known as season cracking. The sessions included six papers, all on brass. During the ensuing 26 yr., many new workers have come into the field and several other metals have been found subject to failure by stress-corrosion cracking when the right combination of stress and environment is achieved. It is not surprising, therefore, that the present symposium has brought forth 29 papers covering alloys of seven important metals. The phenomenon of stress-corrosion cracking is not necessarily confined to these seven metals. Dix3 has stated, "Indeed, it is probable that ingenious investigators can find solutions which will stress-corrosion crack any known metal or alloy." Mears, Brown, and Dix4 have indicated that stress- corrosion cracking failures are not necessarily limited to metals but may include the plastics. It is to be expected that the increase in the number of metals known to crack in service and the general emphasis on such failures at a symposium such as this will alarm many to whom the subject is un- familiar. Such alarm is not justified by the record. It is true that stress-corrosion

Jan 1, 1945

By J. L. Rodda, R. L. Wilcox, E. C. Truesdale

In recent years various problems in connection with research work on the preparation and properties of zinc-base alloys have required reliable information concerning the constitution of the zinc-rich portion of the iron-zinc equilibrium diagram. On numerous occasions rather positive indications were obtained that, for example, the solubility of iron in zinc was incorrectly represented on the current equilibrium diagrams. A careful study of all the available literature relating to the iron-zinc system led to the conclusion that much of the early work was unsatisfactory as measured by present standards of experimental accuracy, and as a result it was decided to redetermine the location of the liquidus curve and of adjacent portions of the diagram. Part I of this paper comprises a description of the experimental methods and a summary of the results by means of which the zinc-rich end of- the iron-zinc diagram has been revised in the following ways: 1. Measurements of the solubility of iron in liquid zinc by several different sampling methods, leading to a relocation of the liquidus curve. 2. Microscopic, conductivity, and X-ray studies of the solid solubility of iron in zinc, which, together with thermal analyses, have resulted in new values for the solid solubility and the eutectic temperature and composition. 3. Heating and cooling curves, obtained by a refined differential method, leading to new locations for the two peritectic horizontals. In Part I1 of the paper the attempt is made to review all of the published work having a bearing on the constitution of the iron-zinc system, and to correlate the present results, and some recently published data involving the use of X-ray technique, with the earlier work, much of which was done from 25 to 30 years ago.

Jan 1, 1936

By J. A. Heskett

NEW ZEALAND is dependent on the outside world for its ferro goods, yet it can boast of at least two well-defined iron-ore deposits; namely, Para Para limonite, 3 Fe203 + 21120 also found as lower hydrated oxides, and Taranaki iron-sand, a combined magnetite and ilmenite, 2FeO + 2Fe203 + FeO + Ti02. The former is of massive variety and the FIG. 1.-VIEW OF WORKS SHOWING IRON-SAND DEPOSITS, ALSO WHARF AND BREAK¬WATER IN THE DISTANCE. latter granular and mixed with various proportions of fine shell and siliceous sand well water-worn. This latter deposit forms the greater portion of the beach sands of the west coast of the North Island of New Zealand. It is so fine that the whole of a sample passed through a sieve of 40 meshes to the inch. The ilmenite cannot be detected by the microscope, as in the titaniferous ores of the Adirondacks, nor can it be magnetically separated, as in the titaniferous ore of Natashkwan, Canada. To all appearances it is a chemical compound of the double oxides of iron and titanium and not a mechanical mixture, as is the ore of the Adirondack deposits.

Jan 8, 1920

By F. W. Maclennan

The following is a list of members who died in 1929. It is compiled from reports to the Secretary's office. Biographical sketches published in Mining and Metallurgy are indicated in the last two columns. Issue Containing Year of Date of Biography Election Name Death 1929 Page 1922 Adams, Waldo Peck................................ June 2 September 435 1903 Argall, Joseph.................................... Nov. 1 1894 Austin, Leonard S................................. Oct. 30 December 580 1905 Bailed, Melbourne.........................Dec. 12 May* 280 1890 Barringer, Daniel M.............................. Nov. 30 February* 119 1895 Batchelleb, HENRr R.............................. Jan. 15 March 167 BINGHAM Charles E............................. 1923 Bibkett, E. H..................................... Apr. 23 August 394 1913 Bibbell, Robert W................................. Jan. 18 April 214 1926 Blackmar, Don C.................................. June 4 March* 189 1920 Bosworth, T. O.................................... Jan. 18 April 214 1894 Boucher, Arthur S..........................Jan. 6 May 257 1927 Brandenthaler, R. R.............................. Dec. 14 January* 64 1889 Bretherton, S. E............................... Oct. 4 December 581 1911 Brunton, F. K................ .. Aug. 17 1924 Brush, Charles F................................. June 15 September 436 1925 Cameron, Frank N........................May 16 July 349 1891 Chambers, Robert E.............................. May July 348 1908 Clark, J. Murray................................. Dec. 3 August* 407 1883 Clymer, edward T............................. Oct. 13 December 579 1914 Cofpey, George T................................. May 8 July 349 1901 Cooke, L. H....................................... Aug. 23 November 537 1915 Cousins, George W........................ June 30 February* 118 1886 Cowles, A. H...................................... Aug. 13 September 436 1892 Crane, Theron I............................. Nov. 2 December 579 1921 Crowell, Samuel B................................ Dec. 9 January* 64 1907 Curtis, Bracey.................................... Jan. 31 April 215 1895 de Batz, Rene........ ............... January March* 189 1928 Dines, Tyson S.................................... March May 257 1909 Dufourco, R. G............................. January November 537 1920 Ericsson, Eric A.................................. Apr. 4 April* 231 1920 Erlenborn, Willi....................... Nov. 10 March* 189 1888 Farish, John B.................................... Nov. 14 December 580 1891 Ferguson, Vincent........................... Mar. 8 May 257 1917 Finucane, T. R.................................... Mar. 22 February* 118 1921 Foch, Ferdinand................................... Mar. 20 1885 Foucar, Edouard I....................... Jan. 3 March 167 1880 Francklyn, Charles G............................. Jan. 11 April 214 1925 Friedl, Arthur J.............................. July 9 September 435 1894 Fuller, James W. Jr............................... April 4 1876 . Goodale, Charles W.............................. April 11 May 258 1912 Graybill, John..........................Dec. 11 June* 320 1887 Gritzner, F. A.................................. Mar. 26 July 394 1906 Gunther, C. Godfrey.............................. Deo. 26 February* 118 1900 Haggen, Edward A.............................. Apr. 22 October 488 1895 Hall, Benjamin M........................Nov. 19 March* 189 1913 Harper, Walter S................................. Feb. 15 August 394 1921 Hawley, William S................................ Apr. 20 June 298 1920 Herd, Walter ... . . . ..... Aug. 23 September 435 1889 Holt, Marmadtjke B............................... Dec. 26 February* 118 1928 Husk, Albert D .... ................June 9 December 580 1920 Hutchinson, S. Pemberton......................... Feb. 16 April 214 1926 Ivanoff, Constantine L............................ Mar. 7 June 298 1914 Jaeger, Frederick..... .............July 28 October 488 1891 Jennings, Robert E.......................Oct. 30 December 580 1922 Johnson, Homar L................................. Sept. 17 October 483 1927 Johnson, Homer H................................. Mar. 21 May 257 1918 Jones, Jesse L ..... ...............Jan. 22 April 214 1892 Jones, Thomas J................................... June 18 October 488 1883 JoOet, Cavalier H................................. Mar. 29 May 258 1881 Kennedy, John S . . . . ... ..........Apr. 22 August 394 1881 Kennedy,- Hugh.................................... May 23 September 435 1895 Kebvin, James H................................... September October 488 1926 Kkom, L. J........................................ Dec. 24 January* 64 1905 La Follette, Harvey M........................... Sept. 19 November 538 1920 MacDonald, Alexander............................ May August 394 1904 Marengo, Paolo................................... May 257 1925 Maxwell, Allison R............................... May 7 November 538

Jan 1, 1930

By Joseph Hyde Pratt, Douglas B. Sterrett, CHAPEL HILL

I. DESCRIPTION. MONAZITE is one of the minerals which, for a long time, was considered rather rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas and Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals, cerium, lanthanum, and didymium (Ce, La, Di)PO;. There is nearly always present a varying but small percentage of thoria, ThO2, and silicic acid, SiO, which are very probably united in the form of a thorium silicate, ThSiO4 Some monazites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent. ; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellow in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a conchoidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that were 6 in. in length. The more perfect crystals are, however,

Jun 1, 1909

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By John A. Gann

The following investigation constitutes a brief réumé of the more important binary magnesium alloys from the standpoint of metallo-graphic technique, and the effect of heat treatment on structure and properties. The comparative newness of the subject justifies this procedure as a preface to a more detailed study of each individual series of alloys. The work was started with the idea of practical application in the industry rather than as a theoretical investigation. The alloy compositions studied were selected as those most likely to show whether heat treatment would produce beneficial results. Furthermore, it was considered satisfactory to use commercial 99.9 per cent. magnesium, the best commercial grade of alloying ingredients, and to limit the time of heat treatment at the expense of incomplete equilibrium. These facts must be kept in mind when examining the results obtained, and the conclusions drawn. Preparation of Alloys All melts were made in an oil-fired cast-steel pot, approximately 12 in. dia, by 12 in. deep. Approximately 15 lb. of flux and 50 lb. of magnesium were melted and the calculated amount of alloying metal was added. After thorough alloying and puddling, the metal was chill cast in a graphite mold with four 1/2 by 1/2 by 4 in. bars fed from a common sprue and runner. The next higher composition alloy in a given series was made by adding the calculated amount of metal to the heel from the preceding cast. The pot was thoroughly cleaned after each series and new flux then introduced, thus avoiding possible contamination from earlier melts. The percentage compositions given in Table 1 are the calculated values. While not all alloys were analyzed, enough were checked to indicate that the reported compositions are correct to a few tenths of one per cent. A more detailed description of the foundry methods employed has been given in a previous paper. 1

Jan 1, 1929

By John A. Gann

The following investigation constitutes a brief réumé of the more important binary magnesium alloys from the standpoint of metallo-graphic technique, and the effect of heat treatment on structure and properties. The comparative newness of the subject justifies this procedure as a preface to a more detailed study of each individual series of alloys. The work was started with the idea of practical application in the industry rather than as a theoretical investigation. The alloy compositions studied were selected as those most likely to show whether heat treatment would produce beneficial results. Furthermore, it was considered satisfactory to use commercial 99.9 per cent. magnesium, the best commercial grade of alloying ingredients, and to limit the time of heat treatment at the expense of incomplete equilibrium. These facts must be kept in mind when examining the results obtained, and the conclusions drawn. Preparation of Alloys All melts were made in an oil-fired cast-steel pot, approximately 12 in. dia, by 12 in. deep. Approximately 15 lb. of flux and 50 lb. of magnesium were melted and the calculated amount of alloying metal was added. After thorough alloying and puddling, the metal was chill cast in a graphite mold with four 1/2 by 1/2 by 4 in. bars fed from a common sprue and runner. The next higher composition alloy in a given series was made by adding the calculated amount of metal to the heel from the preceding cast. The pot was thoroughly cleaned after each series and new flux then introduced, thus avoiding possible contamination from earlier melts. The percentage compositions given in Table 1 are the calculated values. While not all alloys were analyzed, enough were checked to indicate that the reported compositions are correct to a few tenths of one per cent. A more detailed description of the foundry methods employed has been given in a previous paper. 1

Jan 1, 1929

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

THE name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. GEOLOGY The ore deposits of Copper Mountain are related to the Copper Mountain stock, which is an ideal example of the magmatic differentiation in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanics and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial granitization of some of the volcanics. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. THEORETICAL ESTIMATE OF STOPING WITH THE DIAMOND DRILL After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping. Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1945

By M. W. Ditto

THe conversion of the beehive coke plants, in this country, to byproduct plants has been slow, because the coal supplies were near the centers of the steel industry. With the growth of this industry, especially with its development around Chicago, it became necessary to transport large tonnages of coal from the eastern districts and then convert it into coke. The losses due to transportation costs were partly offset by the value of the byproducts recovered. To save the transportation costs, it was desirable that the coal deposits of Indiana and Illinois be utilized. This coal had always been classified as non-coking; it was also considered unsuitable for the metallurgical field because of the high ash and sulfur contents. The conditions, however, were promising enough to start experimental and development work, which crystallized in the design of the Roberts coke oven. The fundamental features of most coke ovens, with respect to the application of heating gas and the recovery of byproducts, are the same and, in the last few years, the tendency has been toward the better application of heating to the walls, higher thermal efficiency, and, by the control of heating conditions, the increase of byproduct yields. Structural features also have been improved and the use of high-grade refractory material has allowed the use of higher temperatures with the resulting higher rated capacity per oven per day. Great improvements have been made in both recuperators and regenerators, particularly with reference to the individualizing of each oven with respect to its adjacent oven, so that each can be operated as a unit if desired. The highest development of the flue type of oven has been applying individual regenerators for the recovery of waste heat. After some research work, it was found that the high-volatile Illinois coals could be utilized for coke by obtaining the better application and control of the heating conditions in the oven. Most of this high-volatile coal that had been used gave a good coke structure under certain conditions. The fact that coke was occasionally made from this coal, demonstrated the possibiity of making coke from it at all times pro-

Jan 1, 1923

By M. W. Ditto

THe conversion of the beehive coke plants, in this country, to byproduct plants has been slow, because the coal supplies were near the centers of the steel industry. With the growth of this industry, especially with its development around Chicago, it became necessary to transport large tonnages of coal from the eastern districts and then convert it into coke. The losses due to transportation costs were partly offset by the value of the byproducts recovered. To save the transportation costs, it was desirable that the coal deposits of Indiana and Illinois be utilized. This coal had always been classified as non-coking; it was also considered unsuitable for the metallurgical field because of the high ash and sulfur contents. The conditions, however, were promising enough to start experimental and development work, which crystallized in the design of the Roberts coke oven. The fundamental features of most coke ovens, with respect to the application of heating gas and the recovery of byproducts, are the same and, in the last few years, the tendency has been toward the better application of heating to the walls, higher thermal efficiency, and, by the control of heating conditions, the increase of byproduct yields. Structural features also have been improved and the use of high-grade refractory material has allowed the use of higher temperatures with the resulting higher rated capacity per oven per day. Great improvements have been made in both recuperators and regenerators, particularly with reference to the individualizing of each oven with respect to its adjacent oven, so that each can be operated as a unit if desired. The highest development of the flue type of oven has been applying individual regenerators for the recovery of waste heat. After some research work, it was found that the high-volatile Illinois coals could be utilized for coke by obtaining the better application and control of the heating conditions in the oven. Most of this high-volatile coal that had been used gave a good coke structure under certain conditions. The fact that coke was occasionally made from this coal, demonstrated the possibiity of making coke from it at all times pro-

Jan 1, 1923

By Edgar L. Weinberg, W. Horatio Brown

The Austinville-Ivanhoe lead-zinc deposit occurs in the Lower Cambrian Shady dolomite. This deposit is located in southwestern Virginia in the faulted and folded Appalachian Valley and Ridge province. The ore bodies resemble the chimmey and manto deposits of northern Mexico and are formed by replacement and filling. They are confined to certain favorable zones of the Austinville and Ribbon members of the Shady. Structural and stratigraphic factors combine to control the location and form of the ore bodies. In certain places secondary oxide enrichment of the zinc minerals has contributed to the economic development of the area. It is concluded that the ore is epigenetic and is deposited by hydrothermal solutions rising through the fault "plumbing." Classification is epithermal-telethermal.

Jan 1, 1968

By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950