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By R. S. French, W. R. Hibbard

M. Balicki—As one who some years ago spent much time searching for an alloy with high thermoelectric power that would be suitable for heat energy-electric energy converter based on the principle of a thermoelectric pile, I would like to make a few comments touching upon that aspect of this excellent paper. The specifications which one of the authors has formulated so aptly do not appear to me as complete, and I would like to add to them the following two demands: (1) Melting point not less than 500°C and (2) elongation on 2 in. at least 5 pct. Condition 1 would insure good thermodynamic efficiency of the pile by permitting a reasonably high temperature of the hot junction and at the same time making it suitable for such application as salvage of vast amounts of energy which is lost in the form of sensible heat of waste gas leaving industrial and other furnaces. Condition 2 is also a very important one; particularly, because of the fact that all elements and alloys which exhibit attractive thermoelectric properties seem to be as a rule very brittle. The design, erection, and maintenance of a pile incorporating a brittle material in one of the most crucial parts of the converter would be a very difficult and costly affair indeed. To illustrate this point I may mention great difficulties I encountered when trying to make thermocouples of silicon. Casting of 1/4-in. rods in iron or graphite mould yielded only broken pieces which had to be welded into a bar. Such a bar had to be handled very carefully during the determinations. Raising the molten silicon by vacuum into a silica tube and solidifying it there solved the problem of stability as well as that of electrical insulation of a bar. On tests this bar (98.5 pct Si) showed dE/dT = — 275.5 microvolts per degree C vs. copper. Thermocouples made of this grade of silicon and pure nickel developed 0.39 v when temperature of the hot junction was approximately 1000°C. The possibility Dr. Gonser has mentioned of trying to impart to metals good thermoelectric properties by alloying them with silicon, has been considered. The preliminary survey which I have made was, however, disappointing. Perhaps, it will be advisable to record the results obtained (table VI), as this might save repetition of search in fields already covered.

Jan 1, 1951

THE book covers principally the assaying of silver and gold and the determination of these values in ores, sweepings, and base metal. It seems to have been written more for the goldsmith and jeweler than for the primary producer of metals. There were approximately sixty different substances needed in the operations described and not over a dozen different types of raw material (ore, matte, crude or alloyed metal) are mentioned. The methods of separation used were essentially simple and reasonably reliable, though the processes were not sufficiently understood to permit the selection of the simplest effective ingredients, and there was a great tendency to employ complicated fluxes, with unnecessary repetition of long-continued heatings indicative of a leisurely pace of life. Practically all the processes described are based on a few chemical facts: the inability of gold to combine with sulphur, while silver and the base metals form easily fusible sulphides; the ready oxidation of base metals; and the ii- solubility of gold in nitric acid. Fluxes serve to make earthy impurities fusible, and to carry oxidizing or sulphurizing ingredients. Many of the processes of assaying had changed little up to the beginning of the present century. Even as late as 1924, when the writer took a University course in fire assaying, the crucibles, cupels, scorifiers, molds, and tongs were identical with those of the sixteenth century, though the wind furnace had a stack on it and the muffle for cupelling was gas-fired.* The fluxes were purer, but of the same essential composition. That this branch- or twig-of metallurgy had not advanced in any funda-

Jan 1, 1949

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By H. M. St. John

MAINTAINING a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in-widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in. any investigation of the various factors that influence the structure and other properties of the casting.

Jan 1, 1930

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y' (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y'. At high temperatures the flow stress is controlled by the amount of Y' in the alloy, i.e., the higher the volume fraction of y', the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y'. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y' has been correlated with changes in distribution of both the dislocations and y'. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y' precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y', based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y' varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y' nickel-base alloys is obtained when the state of dispersion of y' is such that dislocations are forced to cut through the y' particles at the onset of yielding. When the spacing between the y' particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear' in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y' particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested' to account for the temperature insensitivity of the flow stress is the volume fraction of y'. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y' in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y' volume fraction was small (less than 0.2) and the y' particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y' at 900°C was varied from 0 to 100 pct with the y' particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y' and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y' phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y' by volume percent. (The size of the y' particles produced during the equilibrium aging treatment increased as the volume fraction of y' increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y' phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-'. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By Orson Cutler Shepard, Charles F. Skinner

THE leaching method that was first widely used with the cyanide process consisted of percolation leaching of crushed ore in vats or leaching tanks. It was frequently necessary to separate the sand for cyanide treatment and discard the slimes, because only granular material allows the necessary amount of solution to percolate through it in a reasonable time. Later a slime process consisting of agitation followed by thickening and filtration was developed, and is extensively used to the present day. Even though the agitation-leaching slime process is considered satisfactory, the cost of plant and of operation are both greater than for a percolation-leaching plant of equal capacity. This situation has been recognized in the hydrometallurgical treatment of copper-bearing slimes; and a considerable amount of work has been done at the Southwest Experiment Station of the U. S. Bureau of Mines in an effort to develop a percolation method of treating slimes. Experimental work on the copper-leaching problem was started by H. E. Keyes1, and later tests were made by J. D. Sullivan and A. P. Towne2. The Bureau of Mines work resulted in the development of a process by which slimes were moisture-agglomerated with sand and crushed ore, to form a permeable mass through which solution could be trickled without breaking down the glomerules. The agglomeration trickle-leaching method was developed on a small scale and finally tried out in a 12-ton vat. Successful results were obtained as long as the leach solution was added slowly, so that the agglomerated charge was never flooded. If the leach solution flooded the charge, the glomerules broke down and the charge became impervious. There are two important difficulties in the application of the agglomeration trickle-leaching method to the cyanide process for gold and silver ores:

Jan 1, 1937

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1937

By GEORGE D. RAMSAY

ABOUT three miles west of Fontana San Bernardino County, California, and fifty miles east of Los Angeles, the Kaiser Co., Inc., has built an integrated steel plant. By integrated, I mean that from its wholly owned iron ore and coal supply, the Kaiser Co. is producing in its own mills iron and steel products. Pig iron to meet the West Coast needs has been produced at Fontana since Jan. 1, 1943; steel ingots were first poured there May 14, 1943; and steel plate for ships was first rolled Aug. 15, just sixteen months after ground was broken. Briefly, the plant consists of: (I) Two batteries of by-product coke ovens, totalling ninety ovens, carbonizing about 1740 tons of coal per day at capacity; with by-product facilities for the production of tar, ammonia, and ammonium suIphate, light oil distillates, and tar distillates. (2) One blast furnace producing at

Jan 1, 1944

By Orson Shepard

THE leaching method that was first widely used with the cyanide process consisted of percolation leaching of crushed ore in vats or leaching tanks. It was frequently necessary to separate the sand for cyanide treatment and discard the slimes, because only granular material allows the necessary amount of solution to percolate through it in a reasonable time. Later a slime process consisting of agitation followed by thick-ening and filtration was developed, and is extensively used to the pres-ent day. Even though the agitation-leaching slime process is considered satis-factory, the cost of plant and of operation are both greater than for a percolation-leaching plant of equal capacity. This situation has been recognized in the hydrometallurgical treatment of copper-bearing slimes; and a considerable amount of j work has been done at the Southwest Experiment Station of the U. S. Bureau of Mines in an effort to develop a percolation method of treating slimes. Experimental work on the copper-leaching problem was started by H. E. Keyes1, and later tests were made by J. D. Sullivan and A. P. Towne2. The Bureau of Mines work resulted in the development of a process by which slimes were moisture-agglomerated with sand and crushed ore, to form a permeable mass through which solution could be trickled without breaking clown the glomerules. The agglomeration trickle-leaching method was devel-oped on a small scale and finally tried out in a 12-ton vat. Successful results were obtained as long is the leach solution was added slowly, so that the agglomerated charge was never flooded. If the leach solu-tion flooded the charge, the glomerules broke down and, the charge became impervious. There are two important difficulties in the application of the agglom-eration trickle-leaching-method to the cyanide process for gold and silver ores:

Jan 1, 1937

EVERY English-speaking mining, engineer or geologist knows that some terms used by his profession are not rigid but vary regionally; for example: what is called a vein by some, is called a lode by others and is known as a reef to their Australian colleagues. There are parallels in, the German language. Since, in addition, the meaning of some words may change considerably in 450 years-and other words may disappear completely-and not only the terminology but the concepts of a science are subject to drastic changes over such a long period of time, translating the Bergbüchlein posed some interesting problems. Old German texts and glossaries such as C. T. Delius' Anleitung zu der Bergbaukunst (1773), Minerophilus' Neues and Curieuses Bergwercks-Lexicon (1730), and H. Veith's Deutsches Bergwörterbuch (1871) proved useful sources of information when defini¬tions of obscure terms were needed. The task of translating was made even more challenging by the author's personality. As Ulrich Rülein von Kalbe was primarily a physician, his information must have been mostly secondhand. Since the nomenclature of the miners of Saxony, where he gathered his material on silver ores, undoubtedly varied from that of the German miners in Hungary, for instance, who probably supplied him with data on gold ores, it is not astonishing that he is not consistent in his use of some expressions. To give an example: there is every indication that Flöz and schwebender Gang (see footnote p. 21) are used interchangeably in spite of his occasional disapproval of such usage. It is obvious that he was an educated man with a questing and active mind and, although he apologizes-not wholly sincerely, one might suspect-for the simple

Jan 1, 1949

The Development of Research and Quality Control in the Modern Steel Plant. By Leo F. Rein-artz. (Metals Technology, April 1943) Blast Furnace and Raw Materials Essential Considerations in the Design of Blast Furnaces. By A. L. Foell. (,Metals Technology, December 1942) Results Obtained from Surveys of Gas at Furnace Tops. By James M. Stapleton. (Metals Technology, January 1943) Physical Aspects of the Dust Catcher, Gas Washer and Precipitator on No. 3 Furnace at Carrie. By C. P. Clingerman and C. J. FleiscH. (Metals Technology, January 1943) Slag Control by Introduction of Flux through Blast-furnace Tuyeres. By Carl G. Hogberg (Metals Technology, January 1943) The Electrical Conductivity of Molten Blast-furnace Slags. By A. E. MaRtin and GerRard Derge. (Metals Technology, August 1943) Some Physical Characteristics of By-product Coke for Blast Furnaces. By CEarles C. Russell and MichaeL Perch. (Metals Technology, December 19+2) Pyrometry at the Coke Oven. By Robert B. Sosman. (Metals Technology, December 1942) Calcination Rates and Sizing of Blast-furnace Flux. By T. L. Joseph, H. M. Beatty and Gust Ritsianes. (Metals Technology, December 1942) The Low-temperature Gaseous Reduction of a Magnetite. By M. C. Udy and C. H. Lorig. (Metals Technology, October 1942) Steelmaking Problems of Total Operation in Steelmaking. By William C. Marshall and Frank G. Norris. (Metals Technology, April 1943) Silicon-oxygen Equilibria in Liquid Iron, By C. A. ZapFFe and C. E. Sims. (Metals Technology, September 1942) Equilibria of Liquid Iron and Simple Basic and Acid Slags in a Rolating Induction Furnace. By C. R. Taylor and John Chipman. (Metals Technology, September 1942) Rapid Analysis of Oxygen in Molten Iron and Steel. By Gerhard DeRGe. (Metals Technology, January 1943) Silver Chloride as a Medium for Study of Ingot Structures. By Karl L. Fetters and Margaret Dienes. (Metals Technology, August 1943)

Jan 1, 1943

The Development of Research and Quality Control in the Modern Steel Plant. By Leo F. Rein-artz. (Metals Technology, April 1943) Blast Furnace and Raw Materials Essential Considerations in the Design of Blast Furnaces. By A. L. Foell. (,Metals Technology, December 1942) Results Obtained from Surveys of Gas at Furnace Tops. By James M. Stapleton. (Metals Technology, January 1943) Physical Aspects of the Dust Catcher, Gas Washer and Precipitator on No. 3 Furnace at Carrie. By C. P. Clingerman and C. J. FleiscH. (Metals Technology, January 1943) Slag Control by Introduction of Flux through Blast-furnace Tuyeres. By Carl G. Hogberg (Metals Technology, January 1943) The Electrical Conductivity of Molten Blast-furnace Slags. By A. E. MaRtin and GerRard Derge. (Metals Technology, August 1943) Some Physical Characteristics of By-product Coke for Blast Furnaces. By CEarles C. Russell and MichaeL Perch. (Metals Technology, December 19+2) Pyrometry at the Coke Oven. By Robert B. Sosman. (Metals Technology, December 1942) Calcination Rates and Sizing of Blast-furnace Flux. By T. L. Joseph, H. M. Beatty and Gust Ritsianes. (Metals Technology, December 1942) The Low-temperature Gaseous Reduction of a Magnetite. By M. C. Udy and C. H. Lorig. (Metals Technology, October 1942) Steelmaking Problems of Total Operation in Steelmaking. By William C. Marshall and Frank G. Norris. (Metals Technology, April 1943) Silicon-oxygen Equilibria in Liquid Iron, By C. A. ZapFFe and C. E. Sims. (Metals Technology, September 1942) Equilibria of Liquid Iron and Simple Basic and Acid Slags in a Rolating Induction Furnace. By C. R. Taylor and John Chipman. (Metals Technology, September 1942) Rapid Analysis of Oxygen in Molten Iron and Steel. By Gerhard DeRGe. (Metals Technology, January 1943) Silver Chloride as a Medium for Study of Ingot Structures. By Karl L. Fetters and Margaret Dienes. (Metals Technology, August 1943)

Jan 1, 1943

By Michael P. Robinson

It has been suggested that streaming potentials are not nomlally logged because the streaming potentials known to be generated across mud filter cakes are substantially cancelled by streaming potentials generated in contiguous shale beds. Laboratory measuments of streaming poterztials acrons hand specirnens of shale have been adduced as evidence to support the suggestion. The experiments show that streanzing potential depends on the resistivity of the equilibrating solution and on pressure drop. Meizsurenlents were made perpendicular to the bedding planes of the shales. The mechanism of streaming potential generation in shale which the suggested cancellation theory iniplies has been critically examined. Conclusions reached are tested by comparing self potentials logged before and immediately after changing the resistil~ity (but not the weight) of mud in a borehole. The resultant SP change is found to equal the theoretical electrochetnical potential change, i.e., cancellation of .strearning potential is independent of mud resistivity. Since streaming po/entials generateal across mud filter cakes depend critically upon mud reistivity, shale .strearlling potential in situ must he equally sensitive. Using plausible values for the pemleahility, porosiy arzd compressibility of shale, the van Ererdingerl-Hurst approach shows that the pressure drop between horehole pressure and formation pressure in a radially honzogeneous shale is unlikely to coincide with the zone of filtrate invasion. If, perchance. this coincidence occurs with one mud a chatzge 10 a second must result in non-coincidence, i.e., a .YP logged in the second mud should show a streaming potenlial. The dilernrna may he overcome by postrrlating: (I) perrneabilities of shale7 parallel to their beddine planes greatly exceed their cross-bedding permeabilities; (2) a resistivity-sensitive mud cake of low permeability forms either on the face of, or probnhly in the lanlinations of, many shales. These postulates are examined with reference to the pres.sure and SP histories of the McClosky and Aux Vases zones in the Illinois Basin and some srcpport for them found. It is concluded that a definitive solultion to the streaming potential problem does not exist. INTRODUCTION Recently Gondouin and Scala' published a contribution to the streaming potential problem which is notable particularly for the elegance of its experimental techniques. The conclusions drawn by Gondouin and Scala from their studies amplified those previously suggested by Schehck'. In essence they suggested that the streaming potentials known to develop across mud filter cakes" are not normally observed on SP logs because they are largely cancelled by streaming potentials generated in adjacent shales. This suggestion appears so reasonable that many workers in the logging field will be prone to accept it. We incline strongly to the view that the suggestion is basically correct. Nevertheless, it is important to realize that the cancellation hypothesis in the form put forward by Gondouin and Scala does not appear to meet all the known experimental facts. It is the principal intention of this note to call attention to what appears to be a flaw in the relevancy of the experimental evidence adduced by Gondouin and Scala and to suggest an alternative hypothesis to remove it. The consequences of the new hypothesis are compared with field data which, we believe, are unique. A second but not less important purpose of this note is to emphasize that even the new hypothesis does not fully explain all field observations. Hence we conclude that further study of the streaming potential problem is required before it can be said that a definitive solution to it has been attained. The bare experimental bones of laboratory data on streaming potentials appear to be as follows. 1. A streaming potential is developed across a mud filter cake. This streaming potential is virtually independent of cake thickness but depends on the mud resistivity. The relationship is of the form, 2. A streaming potential is developed across a shale. This potential is independent of shale thickness but depends on the resistivity of the permeating solution if the shale has been first equilibrated in this solution. The relationship is of the form, The relationship in (1) was determined first by Wyllie3, confirmed by Gondouin and Scala and qualita-

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1'2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.' Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962

By D. C. McLean

This report summarizes the work that has been done during the past several years in adapting resins for use as auxiliaries in mine roof support. The resins were applied in two ways: 1) by injection into the strata, and 2) as a bonding agent for roof bolts and reinforcing bar. The Explosives and Mining Chemicals Department of the American Cyanamid Co. has worked during this period in cooperation with the Roof Control Research Group of the U.S. Bureau of Mines, the Pattin Manufacturing Co., the J. H. Fletcher Co., the Homestake Mining Co., the U.S. Steel Corp., the National Mines Corp. and the Pocahontas Land Corp. in an effort to create resin formulations and methods for applying them as a practical and sate type of roof support for mining areas particularly where conventional support is inadequate, yet expensive. This, work has involved much pioneering in a field where theory, speculation, and pure mythology predominates, and little basic engineering data is available. It is strange butt true that, despite the importance of roof control both from an operational and safely standpoint, there is scarcely a mining' company in this country that has an engineer, or anyone, assigned to the study of roof support problem, except temporarily--after a bad roof fall. The responsibility for improving roof control methods seems to have been placed entirely upon the shoulder, of the USBM, various State departments of mines, and individual roof bolt manufacturing; companies. It was in cooperation with the USBM that Cyanamid first developed resins for mining use.

Jan 1, 1964

By W. L. Prehn, Adele Chambers, R. L. Slobod

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By R. L. Slobod, W. L. Prehn, Adele Chambers

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By J. W. Pamplin

Some 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.1 Physically the phosphate-bearing formation, locally called the "matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca³P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by 1/2 mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, sometimes a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the "hydraulic line." This 700 yd. of overburden and 300 yd. of matrix—1000 yd. in all-amounts to about 1500 tons of material moved each hour. The overburden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7% long tons in 4000 gal. of water per minute—a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

By J. W. Pamplin

Some 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.1 Physically the phosphate-bearing formation, locally called the "matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca³P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by 1/2 mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, sometimes a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the "hydraulic line." This 700 yd. of overburden and 300 yd. of matrix—1000 yd. in all-amounts to about 1500 tons of material moved each hour. The overburden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7% long tons in 4000 gal. of water per minute—a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

A discussion at a joint meeting of the New York Section of the American Electrochemical Society and the American Institute of Mining Engineers, Nov. 20, 1913. Chairman Lawrence Addicks:-Our program this evening represents an attempt to set before you the present situation and outlook in the metallurgy of zinc. It is a time-honored custom to throw bricks at the zinc man. The accusation is that he has borrowed a lime kiln and a gas retort and part of a sulphuric acid plant, hitched them together, and spent the last 50 years in regarding with holy veneration the reactions which take place in that retort. The copper man, who thinks of zinc as something with which copper is adulterated to make brass, and the iron man, who regards it as a sort of paint for corrugated sheets, and the lead man, whose opinion as to zinc is not fit for publication, have long felt that, when two or three of the minor details of their respective metallurgies were put in order, they would take a few clays and fix up zinc on a modern basis. But somehow there still seem to be some unsolved problems at home, and while we are waiting it seems only fair that the case for the defense should be adequately presented. There is probably no man in this country to-clay better able to do this than Mr. George C. Stone, of the New Jersey Zinc Co., on whom I have pleasure in calling to talk to us on "Progress in the Metallurgy of Zinc." George C. Stone:-It is frequently stated that there has been no change in the metallurgy of zinc since the first Belgian furnaces were built in the early part of the last century. It is true there have been no such spectacular and radical changes as were worked in the metallurgy of copper and iron by the introduction of converters; but, in the essentials, I believe the progress in zinc metallurgy has been as great as in that of the other common metals. The main reason that there have not been revolutionary changes is that the chemistry of zinc differs radically from that of the other metals and these differences control the type of apparatus that can be used. The differences are: 1. The temperature at which zinc is reduced by carbon is much above the volatilizing point of the metal and it is therefore always produced as a vapor.

Jan 1, 1914