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By G. Ostberg

OXYGEN has frequently been considered responsible for phenomena in the metallurgy of cast iron which are not sufficiently explained by the presence of other elements. Oxygen and oxides have been regarded as critical factors, particularly for the solidification process, and specifically in the formation of graphite. However, the evidence for an influence of oxygen has mostly only been indirect or qualitative. Furthermore, quantitative data on the oxygen content of cast iron presented in the literature have often been less conclusive as being apparently determined with insufficient regard for the difficulties associated with the sampling and analysis. These problems, experimental and theoretical, have been studied in this investigation. An attempt is made to bring the views on the soluble amount of oxygen in cast iron on a level with the present understanding of the thermodynamics of these types of alloys. Although there are no experimental data on the complete multicomponent cast-iron alloys some conclusions have been drawn from investigations on simpler systems. The order of magnitude of the solubility of oxygen in cast iron is considered in the first part of the paper. The second part deals with the oxygen content actually present under practical conditions. First the possible sources of errors in sampling and analyzing methods are examined. Finally some observations on the oxygen and oxide content of malleable iron during the production process are made. THERMODYNAMICS OF OXYGEN SOLUBILITY When cast iron is saturated with oxygen the saturation phase is essentially carbon monoxide or silicon dioxide depending upon the composition of the iron, the temperature, and the rates of formation of the oxides.* The latter occurs accordiw to the O + C = CO, Kc0 - a COa J 20 + Si = SiO2, Activities are used here instead of weight pct concentrations, since activities are believed to show more sensitively the effects of the interaction of all the alloying elements. Calculations involving activities are, however, seriously hampered by lack of experimental data on the interactions between the components encountered in the multi component cast-iron system Fe-O-C-Si-Mn-P-S- and so on. In order to make an estimate of the oxygen solubility reason-

Jan 1, 1959

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Walter R. Crane

PAGE I. Apparatus and Methods.......... 406 1. The Magnetic Circuit...........406 2. Apparatus Employed in the Traction-Method...... 406 a. The Coils............409 b. The Pole-Pieces..........409 3. Methods of Testing Fields Produced by Different Pole.Pices.. ..409 c. Testing with a Search.Coil........410 d. Testing with Iron-Filings and Glass Tube.. .. .410 4. General Forma of Pole-Pieces.........411 e. Flat Poles............411 f. Conical Poles........... 411 g. Spherical Poles...........411 h. Chisel-Edged (Chamfered) Poles.......412 II. Magnetic Fields...........412 5. Methods of Testinq for Magnetic Permeability...... 421 i. The Rod-Method..........423 j. Method Employed in These Experiments......424 k. Difference in the Results of the Two Methods..... 425 l. The Traction-Method.........427 m. Effect of Loosening the Charge.......430 n Corrections...........432 6. Theory.............433 o. Effect of Varying Weight on Tractive Force..... 434 p. Effect of Varying Pole-Distance.......436 q. Effect of Varying Magnetization.......436 T. Effect of Varying Size.. .......437 a. Summary,........... 441 III. The Relative Magnetic Permeability of Various Minerals,. 443 The form and strength of magnetic fields have attracted much attention. especially in connection with the designing of dynamo-electric machinery—an art which has been revolution-

Jan 1, 1902

By D. J. McAdam

Results of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station, Annapolis, Md., have been discussed by the writer in several recent paper~.1,2,3,4 In those papers references were also given to the work of Haigh in 1917.= Efforts by the writer to obtain a better understanding of some of the factors involved in corrosion-fatigue finally developed into a general investigation of the effect of time and cyclic stress on corrosion of metals. Corrosion-fatigue of Metals As described in the papers mentioned, rotating-cantilever specimens, conically tapered so that the stress is nearly uniform over a length of about 1.5 in., were subjected to simultaneous fatigue and corrosion. For this purpose a stream of water was diagonally applied so as to sweep the specimen from the outer to the inner fillet and surround the stressed surface with water. The fresh water is a calcium carbonate water, the composition of which has been given in a previous paper.2 The salt water is Severn River water having a saline content about one-third that of sea water. The previous papers described results obtained with ferrous and non-ferrous metals. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at nominal stresses far

By R. L. Loofbourow, Roger V. Pierce

THE degree to which our mineral requirements are being met by mining leaner, more complex or more remote deposits is indicated by developments during 1953. Heavy capital investment, skilled technical advice, planning, and able execution are requirements for the typical venture. Producers, faced with rising costs and with softer prices, are seeking improved mining and recovery. Developments in production of iron ore are typical of the course being followed in metal and nonmetal mining. Iron ore development in the U. S. is concentrated on the spectacular work with Lake Superior taconite, while in Canada new production is expected from Labrador and output from Steep Rock, Algoma, and Newfoundland is being increased. Shipment of iron will soon be made from Venezuela.

Jan 2, 1954

By Robert H. Hafner, Irvin R. Kramer

In recent years considerable interest has been shown in surface-alloyed metals, particnlarly those of chromium (chromized steels), which have excellent corrosion resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high tem- peratures of 1200º to 1400ºC. (2200° to 2550°F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- mon salt, and heated for approximately three hours at 930º to 1040°C. (1700º to 1900ºF.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900º to 1000ºC., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a Chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1943

By Robert H. Hafner, Irvin R. Kramer

In recent years considerable interest has been shown in surface-alloyed metals, particnlarly those of chromium (chromized steels), which have excellent corrosion resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high tem- peratures of 1200º to 1400ºC. (2200° to 2550°F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- mon salt, and heated for approximately three hours at 930º to 1040°C. (1700º to 1900ºF.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900º to 1000ºC., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a Chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1943

By T. A. Rickard

The notion prevails that writing is a knack, that the skilful use of the pen is a gift of nature. This is an error. Dogberry may be responsible for it; he said: "To be a well-informed man is the gift of fortune, but to write and read comes by nature". Because Dogberry said it, we may be sure that Shakespeare thought otherwise. Ability of any sort may be partly innate, but my own observation and experience lead me to conclude that most of the easy writers have become so by constant practice. As I recall the names of men successful with the pen, I remember that most of them have written a great deal and have taken particular pains to improve their style. The suggestion that proficiency in the difficult art is a happy accident provokes a sardonic smile. The larger part of the great writing in our literature is the result of persistent effort. An easy fluency has been the undoing of many; their flamboyant and fantastic scribbling has proved as perishable as froth. This criticism applies to technical writing also; in order that a technical description or discussion may hold the interest of the reader, at least long enough to cause him to read it to the end, the writing must be done carefully and systematically; otherwise it will fail in its purpose of conveying information. Clearness is absolutely essential. "It is not enough to use language that may be understood; it is necessary to use language that must be understood."* The purpose of writing, at least of that which is meant to be read by others, is not only to express ideas but to communicate them. Lack of perspicuity may prove as %ad as

Jan 1, 1931

By G. Horvay, J. G. Henzel

Nomograms and charts are provided which permit rapid determination of the mold-casting interFace temperature and the speed of solidification when a semiinfinite ingot is cast into a semiinfinite mold. The physical properties of the mold, the frozen metal, and the liquid metal are not assumed to be equal, but they are assumed to be temperature independent. The results are correlated with charts prepared by Paschkis and Hlinka—using Columbia University's Analog Computer—for the freezing of finite ingot slabs when a constant surface temperature is impressed, and with experimental cooling curves obtained by Pellini in sand and iron molds for 7 in.-sq steel castings. x = coordinate directed to right of zero (freezing direction) y = coordinate directed to left of zero (melting direction) e = position of freezing front (in x direction) ? = position of melting front (in y direction) $ = temperature (function of position and time) ? = fixed temperature 2L = width of finite slab Y = a fixed position in the semiinfinite mold, or the width of a finite mold (see Section 7) Properties y = density, lb per cu ft c = specific heat, Btu per lb deg F k = conductivity, Btu per ft hr deg F X = heat of fusion, Btu per lb k = k/Yc = temperature diffusivity, sq ft per hr* b - = = - heat diffusivity, Btu per sq ft deg F Vhr Subscripts 2 = pertaining to the still-liquid metal (case of freezing), or the medium which furnishes the heat (case of melting) 1 = pertaining to solidified metal (case of freezing), or to molten metal (case of melting)* 0 = pertaining to mold (case of freezing), or to the still-solid metal (case of melting) f = pertaining to fusion condition (eg.,?f - fusion temperature) i = pertaining to the location x = 0 (the mold-ingot "interface")

Jan 1, 1960

By Kent W. Pilz

Wet dust suppression can be achieved by 1) confinement of the dust within the dust producing area with a curtain of moisture, 2) wetting of the dust by direct contact between the particles and droplets of moisture or 3) the formation of agglomerates too heavy to remain airborne, or too heavy to become airborne, by combining small dust particles with each other and with the droplets of liquid. From the standpoint of economy, availability and safety, water is the ideal fluid; however, it is not as effective for dust suppression as when small percentages of specially formulated dust control compounds are blended with it. Performance of dust control com pounds is related to surface active agents and surface activity. In all liquids there is an attractive force between molecules which varies inversely as the sixth power of the distance between molecules. Thus, in the liquid phase where molecules are crowded together, the intermolecular forces are powerful; whereas in the liquid-vapor phase where the molecules are relatively far apart, these forces diminish rapidly. In the body of a fluid there is an uneven distribution of forces resulting in an inward pull called surface tension. The force which keeps two surfaces apart or causes them to coalesce is termed interfacial tension. Fluids of high surface tension exhibit poor wetting, spreading and penetrating qualities. Water has the unusually high surface tension of 72.75 dynes per cm at 20°C.

Jan 7, 1972

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon' and carbon' on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of' the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon' and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By AIME AIME

THE non-ferrous 'metals industry of the Soviet Union found itself in a very low position at the beginning of the reconstruction period in 1922, due to the absence of modern smelters and the run-down condition of the existing ones. Up to. 1924 there was no great demand for newly smelted non-ferrous metals due to the considerable stocks' of copper, zinc, lead, tin and aluminum in the courtry and also to the undeveloped condition of Soviet industries. However, in 1925 it became necessary to obtain new stocks of non-ferrous metals and in that year 12,000 tons of zinc, 14,000 tons of lead and 2,000 tons of tin and aluminum were imported into the U. S. S. R.

Jan 1, 1929

PROF RICHARD ÅKERMAN Stockholm, Sweden PROF RICHARD BECK Friberg, Germany ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England PROF HANS HOFFER Leoben, Austria PROF HENRI LOUIS LE CHATELIER Paris France M FLORIS OSMOND Paris, France ALEXANDRE POURCEL Paris, France JOHN E. STEAD Middlesborugh, England DR. ING H. C. EMIL SCHROEDTER Dusseldorf, Germany JAMES M. SWANK (Associate) Philadelphia, Pa. PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF TSUNASHIRO WADA Tokyo, Japan CHARLES D WALCOT Washingtion D.C.

Jan 1, 1917

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 J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.' The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov's work.'' He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By Joseph L. Gillson

Bentonite, designating a distinct type of clay, is a young name in mineral nomenclature in the light of the age-old names of most other useful nonmetallics. The earliest references in literature are to "soap clay" (1873) "taylorite" (1888) and finally "bentonite" in 1897, from its occurrence in the Fort Benton series of rocks near Rock Creek, Albany County, Wyoming. Bentonite is a rock term and consists largely of montmorillonite clay. The latter name was proposed in 1847 for a plastic clay found at Montmorillon, France. A clay of apparently identical properties was described by Cronstedt of Sweden in 1788 and a number of other similar clays found in France were given other names in publications from 1853 to 1856. The mineral name montmorillonite was recognized by Dana in 1892. The recognition of "clay mineral" distinctions which led to the present-day classifications of clays by their chief mineral content, dawned in the early part of the twentieth century. Grim6 has aptly said: About 1924, Ross10 and some colleagues of the U. S. Geological Survey began a study of the mineral composition of clays that led to a series of monumental papers on the subject. By the early 1930's what has come to be known as the clay-mineral concept became firmly established in the minds of a great many people actively studying clay materials. The clay mineral concept designates the major clays as kaolins, montmorillonites and illites and by this concept bentonites are now defined as "fine-grained clays containing not less than 85 pct montmorillonite" and a wide variety of clays found all over the world are included in that classification. They could all properly be called "montmorillonite clays" but the common commercial name is bentonite. For a period of over forty years from the time of the earlier discoveries, bentonite was thought to be only the sodium type highswelling clay produced principally in Wyoming. By the clay mineral concept, non-swelling montmorillonite clays also became known as bentonite. In the trade there are two broad divisions-sodium bentonite, often called Wyoming or "western," which expands in water and carries sodium as its predominant exchangeable ion, and calcium bentonite often called "southern," which has negligible swelling and carries calcium as its principal exchangeable ion. There are many intermediate gradations. Properties The mineralogy and chemistry of the clays are so complex that the subject cannot be summarized briefly. The reader is referred to Chapter 12 of this volume in which the subject is treated at some length. Grim6 gave the formula for montmorillonite as (OH)4Si8AL4020.nH2O. He wrote: Montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. . . . Exchangeable rations occur between the silicate layers. . . . The words "tetrahedral" and "octahedral" refer to the coordination number of the cations in the unit cell in the crystallographic lattice. Carroll5a stated: That the montmorillonite structure is the same as that of mica, but the layers are not held together by K+ ions; and water and other polar molecules, such as organic molecules, can enter between the unit layers and cause expansion. Ex-

Jan 1, 1960

By AIME AIME

FRANCIS ANDREW THOMSON was born in London, Dec. 21, 1879, coming to the United States by way of British Columbia where he lived until he matriculated at the Colorado School of Mines. When only sixteen he was inducted into the mining industry as apprentice assayer and millman at the Victoria Metallurgical Works. Following his training at Golden he had more practical mining and milling experience at several properties in the West, and studied a little as well at the Royal School of Mines, in London, and at the Ecole des Mines, in Paris.

Jan 1, 1939

By Earle C. Waite

THE Industrial Minerals Division this year held no individual sessions of its own except the business meeting Tuesday afternoon. One session was held jointly with the Society of Economic Geologists, one with the Milling Methods Committee, and two with the Society of Economic Geologists and the Mining Geology Committee. At all of these meetings the attendance was better than usual and the Tuesday afternoon session, with nearly 400 present, probably set a new record for the Division. Joint sessions seem extremely popular when papers of mutual interest are presented. On Monday afternoon, mica was the predominating subject. The North Carolina mines provided most of the information presented, although the discussion brought out similarities with the New England mines. B. C. Burgess particularly stressed the fact that with the existing curtailment of mica from India it is necessary to get the most mica in the shortest time from the mines in this country. He said that the Colonial Mica Corp. hopes to have 1000 mines operating in the near future. This seems a great number, but when one considers that these mines employ from 3 to 28 men, mostly nearer the low figure, the output of each mine is relatively small. Although the price of mica is from six to ten times the prewar price, the yield of 8 to 150 lb. of mica per ton of raw ore does not provide high returns to the producer.

Jan 1, 1943

By L. D. Jaffe, D. C. Buffum, F. L. Carr

SINCE the temper brittleness of steels is generally considered to be a grain-boundary phenomenon¹,² it would be expected that austenitic grain size would affect temper brittleness. Several investigators"" reported that temper brittleness, as measured by room-temperature impact tests, increased as the austenitiz-ing temperature was raised. It was subsequently pointed out that conclusions as to temper brittleness based upon room-temperature impact tests are likely to be misleading.1,6 Hurlich7 used a range of testing

Jan 1, 1954

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952