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BUFFALO J R Atkinson, Chairman (Hamilton, Ont, Canada) H R Morlock, Secretary CHICAGO H Erler, Chairman (Gary, Ind ) M E Nickel, Vice-Chairman A M Kroner, Secretary-Treasurer CLEVELAND C W Cravens, Chairman (Cleveland) E J Sobey, Vice-Chairman E Kondas, Secretary Leo Svete, Treasurer DETROIT M Groat, Chairman (Ecorse, Mich ) H W Clark, Secretary

Jan 1, 1957

By E. R. Atkins, G. H. Smith

Results of laboratory tests are presented to show that lire value of "m", in the Archie expression dernlined by the shapes of the particles in the system. Tile value of m "the shape factor", is constant for a system of particles of a given shape for a range of F - + values. Applying this concept, one can predict F - + relationships for mixtures of particles with different shapes, and these predicted relationships are useful in electric log interpretation. It is suggested that an equation of the form 1/F -10mcan be used to describe the properties of natural formations containing varying amounts of sand and clay. From this work and values of "a" and "m" reported in the literature, it appears that in many cases rocks in the same geological horizon have a common primary porosity but contain varying amounts of a particular clay. It is concluded that the equation can be applied to a rock-water system only when values of "a" and "m" have been established for the particular system. INTRODUCTION The petroleum literature contains many reports of the results obtained by determining formation resistivity factor F and porosity + of rock samples from oil fields all over the world. The usual practice is to use data from a large number of samples from a number of fields to find an average relationship between F and +. Several such average relationships have been advanced. In the absence of data on a particular formation or field, it has been the practice to use the average relationships to give a rough approximation of the F - + relationship. The purpose of this paper is to report on basic relationships that exist between F and + for naturally occurring particles in water solutions. Other workers' have found the same relationships apply to the diffusion of hydrogen through packed beds of dry particles. In the work discussed here, relationships for application to unconsolidated sands or shales containing mix- tures of particle shapes are derived. These relationships, developed for unconsolidated formations, may apply to consolidated formations. EXPERIMENTAL To evaluate F- relationships for unconsolidated rocks, the results of laboratory measurements on simple slurries of clay or sand will be used. Such laboratory studies are concerned with the electrical behavior of water-containing rocks. The wet rock constituents are electrically similar in slurries and in rocks. Archie2 defined formation resistivity factor as All resistance measurements were made using a 1,000-cycle impedance bridge with an oscilloscope as the null detector." The accuracy of this bridge was better than * 0.15 per cent. For the particular apparatus employed, no additional reactance was required to achieve balance for samples with resistances between

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By Curtis L. Graversen, J. H. Hamilton, John C. Nixon, John R. Lewis

RECENTLY there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1.2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his' paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulfides under varying conditions. To date we have studied the oxidation of galena, 5 sphalerite, and chalcocite. It is a well known fact that copper sulfide minerals are oxidized slowly by weathering agents, so that the sulfides of copper which find their way into a tailing pond are gradually changed into watersoluble and acid-soluble compounds. Commercially, the oxidation of copper sulfide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple-hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°°C. EXPERIMENTAL Preparation of Chalcocite (Cu2S) Natural chalcocite is not pure. Minerals such as bornite, covellite, and chalcopyrite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and finely divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. To this was added a slight excess of

Jan 1, 1948

By W. C. Clarke

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

Jan 1, 1970

By K. P. Anderko

INVESTIGATIONS of the constitution of the system Mg-Ba were first made by Grube and Dietrich1 between 0 and 47 atomic pct Ba and then by Klemm and Dincke1acker" ver the whole composition range. Klemm and Dinckelacker corroborated intermediate phases of the approximate formulas Mg9Ba and Mg4Ba, and showed a third compound to have the formula Mg2Ba, rather than Mg5Ba, as suggested by Grube and Dietrich. Mg2Ba had been previously recognized by Hellner and Laves3 s a MgZn2 (C14) type structure. The main discrepancies between the results of Grube and Dietrich and those of Klemm and Dinckelacker exist, however, in the liquidus temperatures and solidification equilibria of alloys containing more than about 10 atomic pct Ba. The liquidus temperatures measured by Grube and Dietrich, and the outline of the liquidus of Klemm and Dinckelacker are plotted in Fig. 1 on an enlarged scale. Although there are strong reasons to prefer the results of Klemm and Dinckelacker, it was considered worthwhile to remeasure liquidus temperatures of some alloys in the controversial composition range. The alloys, made up from sublimed magnesium and 99.5 wt pct pure barium, were melted in an Armco-iron crucible in a dynamic argon atmosphere. Thermal analyses were taken using a Speedomax auto- matic recorder. Careful stirring during the solidification process was required in order to avoid segregation. After thermal analysis some of the cast alloys were chemically analyzed. The intended and analyzed compositions of the ten alloys prepared are listed in Table I. Since standard barium determinations cannot differentiate between barium present as element and as oxide, both the barium and magnesium contents of the alloys were analyzed. The fact that the sum of barium and magnesium was close to 100 pct in each case was taken as evidence that no excessive oxidation had occurred. The liquidus temperatures measured are listed in Table I and plotted in Fig. 1. As can be seen, they are in good agreement with the liquidus found by Klemm and Dinckelacker. This leaves no doubt that the thermal results of Grube and Dietrich above 10 atomic pct Ba are incorrect. This work was performed under the sponsorship of the Pitman-Dunn Laboratories of Frankford Arsenal, Philadelphia, Contract No. DA-11-022-ORD-1975. Sponsorship and permission to publish by this organization are gratefully acknowledged.

Jan 1, 1958

By M. E. Wadsworth

"For his creative efforts in explaining the electrochemistry of sulfide mineral leaching systems." Leaching reactions that occur during the dissolution of selected base metal sulfides and metals are considered in terms of surface reactions and the influence of intermediate or final products formed. These products may be solid layers, requiring solid phase diffusion for the reaction to proceed, or ions in solution that can influence the kinetics by controlling the mixed potential of the solid. Three general types of reactions are proposed to explain observed rates of reaction. Examples are presented for non-oxidative and oxidative leaching of galena (PbS), anodic dissolution and oxidative leaching of molybdenite (MoS2) and cyanidation of silver and gold.

Jan 1, 1986

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß' and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß' varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By Henry Rawdon

THE METHOD of demonstrating the structure existing in a metal or alloy at high temperatures, by etching a polished sample after it has been heated to the desired temperature, is quite familiar to metallographists. The usual procedure1,2 is to heat the specimen, previously polished for microscopic examination, to the desired temperature, in a neutral atmosphere (hydrogen or nitrogen), then admit the etching gas. (chlorine, hydrochloric acid or similar gas) for. a few seconds, and finally, after flushing out the etching gas with the neutral one, cool the specimen in the neutral atmosphere. The pattern produced by etching at a definite temperature is usually taken as a record of the microstructure prevailing at that temperature. It has frequently been pointed out that changes in composition of the surface metal occur during the preliminary heating in the neutral atmosphere, so that the appearance produced' by the etching at high temperature may not exactly represent the condition of the interior of the specimen. To overcome this uncertainty, the heating has sometimes been done in vacuo,3 the etching gas being ad-mitted when the desired temperature was reached, then pumped out and the specimen cooled in vacuo.

Jan 2, 1920

By Norman B. Pilling

The technical difficulties hampering the metallographic analysis of silicon steels are chiefly the result of the extreme corrodibility of these alloys. The addition of silicon to iron in increasing quantities, up to about 6 per cent., rapidly increases the susceptibility of the alloy to chemical attack, not only in acid solution, but in water. This renders the preparation of metallographic sections very difficult, because of a non-selective attack upon the finely polished surface by the water used as a lubricant in polishing. This water attack masks the true structural details revealed by suitable etching reagents. It is thus necessary to use alcohol as a polishing lubricant in the last stages of preparation and to avoid all etching reagents having an aqueous base. A specific reagent for the identification of iron carbide in ferrous alloys, and the one hitherto used almost' exclusively by metallurgists, is an alkaline aqueous solution of sodium picrate, which stains this constituent selectively. Its application to silicon steels has not proved successful, as its distinctive selective action is more or less completely hidden by the general attack of the aqueous solvent on the silico-ferrite, greatly accentuated by the fact that this reagent must be used at its boiling temperature (105' C.). Thus, a powerful metallographic aid to the study of the higher silicon alloys, such as transformer steels, is lost. A new reagent has been developed for the purpose of overcoming this difficulty. It is with some hesitation that the list of etching reagents, already overburdened, is increased, but the properties of this new reagent are advantageous in several ways and a definite field for it may be found in the metallography of ferrous alloys. The reagent consists of a dilute solution of nitric acid and methyl alcohol in nitrobenzol. It is a great advantage to secure an anhydrous solution, as a tendency toward acidic etching has been traced to small amounts of water. A convenient method of preparation is to make an anhydrous stock solution of nitric acid in methyl alcohol in the proportion 20 per cent. acid by weight (12.5 per cent. by volume). The alcohol can

Jan 1, 1924

By L. H. Reiss, J. Groult, L. Montadert

Many fields, where the reservoir is composed of sandy layers, show great complexity because of the lack of continuity which results from a particular type of seditnentation. This complexity may be a factor of prime importance in studying reservoir drainage, especially in the displacement of oil by water or gas. This paper describes work done to study this heterogeneity and its influence in the exploitation of the fields of the lower Devonian sandy shale in the Fort Polignac Basin in Algeria. Two lines of research were followed. 1. On the border of the hasin, a detailed sedimentological study established rules for the distribution of the sandy zones, which furnished hypotheses necessary for devising a geologic model of the reservoir. A certain number of sandy zones were recognized and characterized by their sedimentation. 2. In the interior of the basin, production logs deterrnined the productivity profile. Study of these point data led to a description of the distribution of oil and gas phases in the reservoir so that the continuity of different zones between the wells could be deduced. These techniques were applied to the study of the lower Devonian sandy shale reservoir of Zarzaitine. The sedimentological study guiding the correlation work, with the aid of the conventional static data (logs and cores), led to the establishment of a useful geologic model of the reservoir. Production logs, thanks to the contribution of dynamic elements, permitted corrobora-tion of the model. In particular, the logs confirmed separation, as proposed by the sedimenfological study, of two comparable sandy groups by revealing the continuity of a thin impermeable layer, invisible on conventional logs. INTRODUCTION The heterogeneity of sandstone reservoirs considerably influences the distribution of fluids, as well as their displacement in the reservoir. Rational development of a field and maximum recovery of hydrocarbons are closely tied to an exact and precise knowledge of the intern architecture. We will try to show how it is possible I refine the knowledge of the reservoir by seeking qui different and varied sources of information. Productic geology, the group of techniques which leads to idei concerning reservoir architecture and its geometric descris tion, furnishes the framework of this undertaking. Of these techniques. those used so far are qui varied. Descriptive as well as quantitative, the technique partake as much of classical geology as of reservo science. They include (1) geologic studies of the enti basin, especially a stratigraphic and sedimentologic study of the reservoir member at its outcrop, detail1 observations of cores taken from wells and, finall oriented cores; (2) interpretation of geophysical dat (3) interpretation of electric logs, nuclear and sonic lo and dipmeters: (4) petrophysical study of the reserve on samples taken from wells; (5) reservoir dynamics (stu of the production history and, in particular, interpretati of production logs); and (6) analysis of the fluids a thermodynamic studies. This incomplete list could also include (1) study the migration of the fluids, (2) geochemistry (chemi characterization of the oils), (3) regional hydrodynamii and (4) injection and detection of tracers. If most of these techniques are classic, attention i nevertheless be called to applying two of the techniql in conjunction: the study of the reservoir member its outcrop and the study of dynamic distribution fluid phases in the reservoir through use of product logs, used in the study of the sandy shale reservoirs the lower Devonian of the Fort Polignac Basin, Alge in particular, their application to the study of the 2 zaitine field where they have led to a new and satisfact model of the reservoir will be described. THE ZARZAITlNE FIELD Situated in the interior of the Fort Polignac 8 about 150 kilometers (km) north of the lower Devol outcrop, the Zarzaitine Devonian oil field was discovc On Ian. 28, 19'' (Figs. 1 and l8). It is in the fern a monocline truncated by two perpendicular fault: great throw, with a downthrown section to the north\: Erosion at the top of the structure has caused one of it to disappear. It is a reservoir with a gas cap an m coefficient on the order of 1:5, open to the aql On the northeast, with the oil zone covering an Of 106 sq km and with initial oil reserves of 222 mi

Jan 1, 1967

By E. H. Jr. Dix

THE work of Merica1 and other investigators indicates that the phenomenon of age-hardening in. alloys of the duralumin type is primarily dependent upon the variation in the solubility of copper with temperature. In addition to copper, however, these alloys contain small amounts of magnesium, silicon, manganese and iron, which may affect the age-hardening either directly or indirectly. The effect of these elements on the solubility of copper and on the manner in which this solubility varies with the temperature is of considerable interest, therefore. The effect of magnesium is of especial interest because apparently it exerts a marked effect on the natural or room-temperature aging of alloys of the type described.2 A series of investigations3 has been in progress in the research laboratories of the Aluminum. Company of America to determine the functions

Jan 1, 1932

[Paragraph No. PREFACE ON ASSAYING I BALANCES AND WEIGHTS 2 Balances required for Assaying 13 How assay Weights are made 3 Assay Weights based on the Centner 18]

Jan 1, 1949

By Milton E. Wadsworth, Edward M. Eyring

BETTER understanding of solid surfaces and their associated adsorption products is of both academic and practical value. The study of detergents and their behavior in cleaning surfaces is fundamentally related to the nature of the products adsorbed and their ability to compete for certain surfaces. Similarly in flotation, the nature of the adsorbate before and after adsorption is basic to clear understanding of the process. The recently developed pellet technique1,2 employing infrared spectroscopy provides a powerful tool for the study of solid surfaces. Absorption bands, which are infrared-active, may be observed for adsorbed products. Also any changes in the surface substrate that occur as a result of adsorption may be detected by means of differential spectra. In applying the pellet technique to solids of large surface area, French and his coworkers3 have surveyed the adsorption of organic flocculants on clay minerals, oleic acid on fluorite, and ammonia on cracking catalysts. Recent work on application of differential infrared spectroscopy to the study of solid surfaces' has demonstrated that the difference between a sample and a reference can be obtained with double-beam instrumentation. In this way displacement of surface products, adsorption of new products, and differences in the substrate, if any, may be detected. Experimental Procedure: Potassium iodide pellets were used in this study, prepared from recrystallized analytical reagent grade KI. Grinding was carried out in a Fisher mechanical agate mortar. Two-gram plates containing the solid under study were pressed in a special evacuated die constructed in the laboratory at the University of Utah." Concentration depended on the solid in question. Zinc sulfide and willemite are sufficiently transpar- ent in the infrared region for concentrations as high as 20 mg of mineral in 2g of KI to be used. Zinc oxide is even more transparent, permitting concentrations as high as 60 mg in a 2-g plate. For non-differential operation, however, much lower concentrations (2 to 10mg/2g KI) had to be used. Spectra were obtained on a Per kin-Elmer 21 double-beam recording infrared spectrophotometer. A sodium chloride prism was used giving a spectral range of approximately 2 to 15 v wave length. For differential runs a resolution of 1000 was used and the scanning speed was controlled commensurate with instrument response. The response was checked continuously and each spectrum was repeated several times. For nondifferential runs a resolution of 927 was used. Zinc oxide used was analytical grade oxide fume. The zinc sulfide was precipitated from solution with analytical grade zinc sulfate and sodium sulfide. The precipitate was washed and centrifuged several times and dried. Before use the precipitate was washed in dilute HCl and then treated with saturated NH4Cl to remove any bulk oxides and sulfates. X-ray patterns of the precipitate were comparable to that of the natural mineral sphalerite. The precipitate was much more satisfactory than finely ground natural ZnS because of its very large surface

Jan 1, 1957

By Wilfrid R. Foster

The industrial importance of the sillimanite group of minerals depends upon the beneficial properties exhibited by porcelains and refractories in which substantial amounts of these minerals are utilized as raw materials. The presence of "sillimanite" (now known to be the closely related mineral, mullite) in conventional porcelains and refractories has been known since before the turn of the century. As early as 1906 German investigators observed a direct correlation between the "sillimanite" content of a porcelain and its electrical and mechanical properties. Acting upon this discovery, U. S. Bureau of Standards investigators during World War I developed improved pyrometer tubes and spark plug porcelains, by increasing substantially the amount of "sillimanite" at the expense of quartz. The success of these experiments, first reported in 1918, at once aroused a lively interest in the location of natural sources of sillimanite and its related minerals. As a result of diligent search, the large andalusite deposits in California were discovered in 1919. Within the next several years large deposits of kyanite and sillimanite in India and kyanite in the United States had been reported. The search for these minerals in quantity, by both private and governmental agencies, has continued unabated during the ensuing forty years. A number of domestic deposits of kyanite have been worked during the past 30 years. Of these, only the Virginian and South Carolinian deposits are currently in substantial production. The only commercial andalusite production in the United States has been in California and Nevada. A dumortierite deposit in Nevada, known since 1917 but ignored for want of a commercial use, began production in 1925. A topaz occurrence in South Carolina has yielded a small production since about 1940. Domestic production of andalusite, dumortierite and topaz had virtually ceased by 1950. There has never been any commercial development of domestic sillimanite deposits. Kyanite has been mined almost continuously in India since about 1922. The remoteness of the large deposits of Indian sillimanite had caused it to be neglected until 1949. In that year sillimanite production began, and it has continued to the present. South African andalusite has been marketed from the 1930's until the present time. From 1944 to 1955 Kenya, British East Africa, was an important producer of kyanite. Commercial deposits of kyanite in Ontario, Canada should soon be in production. The first production of kyanite in Europe began in Austria in 1953. No commercial deposits of mullite are known anywhere in the world. It is of interest to note that synthetic mullite, which as "sillimanite" first elicited interest in the A12O3-rich aluminosilicate refractories, has enjoyed a marked increase in production in recent years. This is a result of the gradual depletion of known deposits of high-quality kyanite and related minerals."' Composition The sillimanite group includes kyanite, andalusite, and sillimanite, all having the same chemical composition (A12O3•SiO2) but different physical properties. Two other minerals, dumortierite and topaz, are also included in

Jan 1, 1960

By W. P. Sykes

In connection with a study of tungsten steels, Honda and Murakamil reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. Materials The iron powder used in preparing the alloys was obtained as follows : Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000" C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 per cent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon. The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly for several days at temperatures up to 1500' C. and for shorter periods

Jan 1, 1926

By A. J. Garnier, N. H. van Lingen

Rock downhole is known to be lesc. drillable than when brought to the surface. This must be ascribed mainly to the presence under downhole conditions of a pressure differential across already made chips, which hinders their being lifted. The pressure differential has partly a static and partly a dynamic origin. Balling-up of bits is another consequence of this pressure differerztial. Reduction in penetration rate owing to an increase in the strength of the rock is governed by the difference between the mud pressure and the pressure of the for/nation pore liquid. Rotationally symmetric geostatic stresses have 170 effect on drillability. Fracture of rock when drilling will be brille in most cases. The above is supported by laboratory drilling experiments with drag bill and roller bits an elevated mud, pore, and confining pressures On rocks differing in strength and permeability. INTRODUCTION In oil well drilling drillability of rock is found to decrease with increasing depth of the hole. Naturally deep rock will be more compacted and, therefore, harder to drill than shallow rock of the same type. However, apart from this the drillability of a sample of deep and compacted rock brought to the surface is generally much higher than in its original location downhole. In view of the economic implications of this reduction in drillability, it seems worthwhile to analyze its causes. The origin clearly has to be sought in the difference of environment. The only conceivable factors would seem to be the presence of mud under pressure, the pressure of the formation pore liquid, and the overburden of the rock. Down the borehole the rock is compressed triaxially by mud pressure and overburden. It is well known that the strength of rock is increased when confined by external pressure1. Various authors have, therefore, ascribed the difference in drillability mainly to the strengthening of rock by triaxial compression. Another factor, mentioned by Bobo and Hoch5, is that forces. including "pressure differential forces", tend to hold a dislodged particle in place. However, the conditions determining their magnitude are not clarified nor is their effect on drilling rate assessed. In the laboratory, drilling experiments on pressurized samples of rock yielded evidence that pressure differential forces holding the chips down are the major factor in reducing rate at depth. This paper describes the experiments and shows how the results enable both a qualitative and a quantitative interpretation of the factors determining the effect of chip hold-down on drilling rate. The implication with respect to balling-up and jet action is also discussed. The greatcr part of the experiments were performed in the pressure vessel shown in Fig. 1. The spacc between the sample of rock and the vesscl is divided by "0" rings into three separate chambers. The rock sample is confined laterally by pressurized oil in thc middle chamber. Penetration of oil into the sample is prevented by partly jacketing it with brass foil. Thc pressure of the drilling fluid in the hole can be adjusted via the upper chamber. Permeable rock specimens arc water saturated before being drilled. With a properly plastering mud as drilling fluid the pressure of the pore water can be adjusted independently via the lower chamber.

By B. H. Kear, H. G. F. Wilsdorf

After a few percent strain, dislocations in disordered Cu3Au are arranged in groups in ulell-defined slip planes, which contrasts with the more or less random distribution of dislocations in the corresponding ordered alloy. Unusually long and straigkt dislocation segments observed in the ordered alloy are interpreted in terms of cross slip of screw dislocations from their slip planes into cube planes. It is proposed that cross slip, and also dislocation reactions of the Lomer type, play an important role in work hardening of the ordered alloy. ACCORDING to to dislocations in the disordered lattice are only partial dislocations in the corresponding super lattice, so that in the super-lattice dislocations must occur as pairs, with each pair connected by a ribbon of antiphase boundary. Recently, striking confirmation of the theory was obtained by Marcinkowski, Brown, and Fisher3j4 in a study of dislocation configurations in thin foils of the Cu3Au alloy by transmission electron microscopy. In the present investigation, the observations made by these workers have largely been confirmed. Moreover, it has been found that dislocations in the plastically deformed ordered alloys are often unusually long and straight. This paper is mainly concerned with these new observations. A tentative explanation is offered in terms of cross slip of dislocations in the ordered alloys. PREPARATION OF SPECIMENS An alloy close to the stoichiometric composition Cu3Au was prepared by melting together high-purity copper and gold (99.995 pct) under vacuum in a graphite mold. The resulting ingot was rolled down and cut into strips 1 1/2 by 1/8 by 0.005 in. in thickness. All strips were annealed at 900°C for 3 hr and cooled to 500'~. A few of the strips were quenched from ~OO'C, while the remainder were slowly cooled in the temperature range 400" to 150°C at intervals of a few degrees every 24 hr to produce a high degree of order. After this annealing treatment the average grain size of the material was about 0.1 mm. Material in different states of order was obtained by reannealing fully ordered material at temperatures below the critical temperature: followed by quenching. The equilibrium degree of order attained at a particular reannealing temperature was obtained from the paper by Keating and warren.' A simple hand-operated tensile jig was used to give the strips the required amounts of plastic strain. Following straining, a number of specimens were cut from each strip by means of an electrolytic cutting device.= Finally, each specimen was thinned electrolytically using the polishing procedure described by Bakish and Robertson,7 and these thin sections were examined in the Philips EM-100B electron microscope operating at 100 kv. EXPERIMENTAL OBSERVATIONS Antiphase boundaries. The average domain size in the ordered alloys was found by direct observation to be about 0.25 p. Also, it was observed that the grown-in configuration of antiphase boundaries was changed little by plastic deformation, at least up to 6 pct strain. Fig. 1 shows an electron micrograph of a thin foil of partially ordered alloy (S - 0.8) after 3 pct strain. The micrograph shows a few dislocation pairs and a somewhat crystallo-graphic network of antiphase boundaries. The normal to this foil was found by diffraction analysis to be approximately 11121, with principal directions in

Jan 1, 1962

By W. F. Stowasser

Robert E. Hagen (Oliver Iron Mining Div., U. S. Steel Corp.)—Mr. Stowasser and his associates are to be congratulated on their achievements in developing the design of a pilot agglomerating plant, based on information obtained from experiments made in a laboratory sinter pot, and subsequently constructing and successfully operating this plant. In his Transactions article, May 1955 (vol. 201) Mr. Stowasser stated that the output of his heat treating strand was about 2 Lt per sq ft of grate area per day and that the fuel consumption was 0.7 to 0.8 million Btu per Lt of product. If it is assumed that the burning zone extends from the back of the ignition furnace to the beginning of the recuperation windbox, only about 1/3 of the grate area over the windboxes is utilized for burning pellets, and the actual rate at which partially dried pellets are burned is about 6 Lt per sq ft of grate area per day. It may be interesting to compare the above operating data with that obtained at the Extaca plant, where taconite concentrate is treated on a conventional sin- tering machine using limestone or hydrated lime additives with no recuperation of heat. The entire windbox area is used for burning, and a production rate of 2.5 Lt per sq ft of windbox area per day has been attained at a fuel consumption of 1.8 to 2.0 million Btu per Lt of product, the latter being considerably in excess of that reported by Mr. Stowasser, partly because a circulating load of returns amounting to 28 to 30 pct of the machine feed is used and because no attempt is made to recuperate heat from the waste gases. With the high capital and labor costs prevailing today, it seems that future development of the downdraft grate pelletizing process should be directed toward taking advantage of the high burning rate of predried pellets and increasing capacity, perhaps at the expense of fuel economy, by decreasing the proportion of grate area utilized by ancillary functions. For example, eliminating the cooling zone and using this area for burning would increase the proportion of grate area available for burning from 33 to 50 pct of the total windbox area, and a proportionate increase in capacity would result.

Jan 1, 1956

Abbey, Robert Graham, District Mgr.. The W. W. Sly Mfg. Co., 50 Church St.. New York, N. Y. '21 Abbott, A. N., Mines Supt., Mazapil Copper Co., LtdConcepcion del Oro, Zac., Mexico. '28 *Abbott, Argyle Campbell, Dev. Dept., E. I. du Pont de Nemours & Co., Wilmington, Del. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg.. Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Elkhorn Div., Consolidation Coal Co., Jenkins, Ky. '16 Abeel, George H., Jr., Cons. Min. Engr Box 427, Santa Monica, Cal. '18 Abel, Albert E., Asst. to Pres., Valley Mould & Iron Corp Hubbard, Ohio. '19 Abel, Raymond L., Asst. Prof., Dept. of Pet. Refin., Univ. of Pittsburgh Pittsburgh. Pa. '28 Abeel, Leo M., Research Engr., Sullivan Concentrator Chapman Camp, B. C., Canada. '31

Jan 1, 1929