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By Alexander Squire

One of the principal factors that have contributed to the hesitancy of design engineers to use metal-powder parts is the difficulty experienced in the determination of the mechanical properties of compacted components. Because standard test methods cannot usually be applied in the inspection of such parts, and because adequate special test methods have not been developed, it has been considered desirable to investigate the methods that are applicable. These may then be included in specifications for metal-powder materials and components in order that the design engineer may be assured that the subject parts possess the desired mechanical properties for satisfactory performance. It is known that direct relationships exist between usually nonmeasurable properties as tensile strength and elongation and shear strength and the angle through which compacts may be plastically deformed before fracturing. These correlations are valuable in the inspection of specific parts, but it is necessary to set up standards before they may be satisfactorily employed. Apart from the use of correlations, the number and character of the inspection methods that are applicable to almost all powder parts is limited to three—chemical analysis, density, and hardness. The last of these may or may not be a pertinent characteristic, since the indentation hardness of many powdeied-metal materials is so low as to have little significance. It is, however, occasionally desirable to use hardness measurements as an indication of the uniformity of the structure of pieces of a given type. Chemical analysis reveals very little about the physical properties of metal-powder compacts, since the unpressed powder is usually of a composition almost identical with that of the finished pieces. Density determinations are simple to perform and have the advantage of being nondestructive in character. If the dimensions of a machine part are known (and usually they are), the average density may be determined by weighing a given number of pieces and dividing by the calculated volume of the parts. More accurate measurements may be made by the water-displacement method. It is recognized that mechanical properties of metal-powder materials are related to their density, but usually these relations are determined for only one type of powder, processed under a given set of conditions. Comparisons of the pioperties of compacts formed from different types of powders are made on the basis of compacting pressures instead of density, and for this reason the results obtained by using powders of different types appear widely variant.

Jan 1, 1947

By Charles S. Barrett

This paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstruc-tures. About 1200 exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,' and a number of these have been selected to illustrate the results obtained. prints are also included showing the common types of falsities—to borrow a term from the biological field, the "artifacts." ln brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. In addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains, since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. Specimen Preparation and Photographs Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for these polishing and etching (each successive polish becoming less severe and each etch lighter), since the fina1 etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and 16, the replicas used were of silica, deposited upon polystyrene and floated from the polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1944

By Charles S. Barrett

This paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstruc-tures. About 1200 exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,' and a number of these have been selected to illustrate the results obtained. prints are also included showing the common types of falsities—to borrow a term from the biological field, the "artifacts." ln brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. In addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains, since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. Specimen Preparation and Photographs Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for these polishing and etching (each successive polish becoming less severe and each etch lighter), since the fina1 etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and 16, the replicas used were of silica, deposited upon polystyrene and floated from the polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1944

By R. C. Schmidt, B. E. Kennedy

The Mont Klahoyo magnetite deposit is located about 600 km (373 miles) northwest of Abidjan, Ivory Coast. During an exploration period ending in 1977 an international joint venture group investigated the deposit and proved reserves of 670 Mt (739 million short tons) grading 36% iron. The deposit occurs at the northeast end of the Baoubly-Kiriao chain of Precambrian iron formations with associated amphibolites, pyroxenites, and gneisses of the Liberian Shield. The ore body is represented by a highly metamorphosed banded quartz-magnetite iron formation with alternating beds of iron silicates and quartz-magnetite. Amphibolite-pyroxenites and sillimanite-cordierite-garnet gneisses form hanging and footwall rocks. The iron formation has been folded into an elongated, overturned 2-shaped major drag fold with axes trending and plunging approximately northeast. Beds are vertical or dip steeply to the southeast. The ore zone has an average thickness of 130 m (427 ft) and outcrops intermittently over a distance of approximately 5.5 km (3.4 miles). Based upon detailed studies of drill cores and the results of ore dressing test work, eight stratigraphic units, identified as K- 1 to K-8, are recognizable in the iron formation. Four interbedded units are low grade silicate zones (silicate facies) while the remaining quartz-magnetite units are oxide facies, representing the important Mont Klahoyo deposit ores. Ore-bearing "K" units are subdivided further into 11 ore types, based upon their specific lithologies, iron content, and concentration characteristics. Identification of these ore types proved particularly useful to mine planning and flowsheet design. A cap of oxidized material overlies the primary quartz- magnetite iron formation, but no enrichment has occurred. It is thought that the Mont Klahoyo iron formations were deposited chemically in a volcanic environment as a siliceous iron formation with volcanism the primary source of iron and silica. Metamorphism converted the siliceous iron formation to a coarse-grained, quartz-magnetite-silicate iron formation.

Jan 1, 1983

By A. A. Scheil, S. I. Hoyt

In technological studies on steel considerable emphasis has been placed on the identification of the foreign inclusions, testimony of which is adequately given in the metallographic literature covering methods for their identification. The outstanding accomplishment in this field is the scheme devised by Campbell, Comstock and Wohrman for identifying various oxides, sulfides, silicates and other constituents by systematic etching tests and microscopic examination.' The time involved in carrying out this procedure has led to attempts to secure quicker methods, or at least to shorten the time required to secure essential information. An example of this is the use of dark field illuminatin,2 but when this was tried out by the authors it was found that cavities and pits on the polished surface appeared bright on a dark field and could not be distinguished from small glassy inclusions. Still another means is the Leitz Ultropak, an instrument equipped with optical units for the illumination of the specimen by reflected light to secure an effect similar to dark field illumination. The structures are made visible in exceedingly sharp details by utilizing the inherent properties of the samples, such as refractive index, absorption coefficients and reflection powers. We have had no experience with the Ultropak, but a recent paper by Benedicks and Löfquist3 describes methods for determining the refractive index of (Fe, Mn) O and MnS by the use of this equipment. Presumably this method would be subject to about the same limitations as dark field illumination, though the, feature added by Benedicks and Löfquist appears to offer great promise in inclusion identification.

Jan 1, 1935

By A. A. Scheil, S. I. Hoyt

In technological studies on steel considerable emphasis has been placed on the identification of the foreign inclusions, testimony of which is adequately given in the metallographic literature covering methods for their identification. The outstanding accomplishment in this field is the scheme devised by Campbell, Comstock and Wohrman for identifying various oxides, sulfides, silicates and other constituents by systematic etching tests and microscopic examination.' The time involved in carrying out this procedure has led to attempts to secure quicker methods, or at least to shorten the time required to secure essential information. An example of this is the use of dark field illuminatin,2 but when this was tried out by the authors it was found that cavities and pits on the polished surface appeared bright on a dark field and could not be distinguished from small glassy inclusions. Still another means is the Leitz Ultropak, an instrument equipped with optical units for the illumination of the specimen by reflected light to secure an effect similar to dark field illumination. The structures are made visible in exceedingly sharp details by utilizing the inherent properties of the samples, such as refractive index, absorption coefficients and reflection powers. We have had no experience with the Ultropak, but a recent paper by Benedicks and Löfquist3 describes methods for determining the refractive index of (Fe, Mn) O and MnS by the use of this equipment. Presumably this method would be subject to about the same limitations as dark field illumination, though the, feature added by Benedicks and Löfquist appears to offer great promise in inclusion identification.

Jan 1, 1935

By Norman Weiss

IF we were to measure progress this year in terms of large new mills and discoveries of fundamental significance we should certainly be disappointed. Outside of the uranium field there was little of a spectacular nature. San Manuel and Reserve completed their first year of operation; Erie approached readiness; the Toquepala project in southern Peru broke ground and gained speed. Important mill enlargements occurred at Inspiration, Anaconda, Ray, and Climax Molybdenum. A 3000-ton copper concentrator was completed at Pima, near Tucson. The Republic Mill of Marquette Iron Mining Co. started up in April. Abroad, the great developments in the African Copper Belt can be likened to the rapid growth of the porphyry coppers in this country. Fundamental research was confined nearly entirely to iron ore flotation and recovery of metal values from leach solutions, particularly uranium. The large number of review articles this year reflected a desire to take stock and consolidate past gains before taking the next bold steps. Undoubtedly a shortage of competent young engineers and technicians is stunting the natural growth of theoretical investigation in the field of minerals beneficiation, as well as the conversion of ideas into action. We find our small stock of talented young scientists concentrated in a few centers of erudition because there are not enough to diffuse through the industry. It is safe to say that among mine administrators and managers there is more interest in the education, training, and welfare of the young engineer than ever before.

Jan 2, 1957

By B. Bernstrom

A 22-ft diam, 7-ft long, wet autogenous grinding mill was installed in the new Cretaceous plant of the Jones & Laughlin Steel Corp. to prepare crude iron ore for concentration in spirals and flotation cells. The paper describes the flowsheet and gives a description of the operating and metallurgical results that have been obtained. These results include capacity, horsepower, operating problems and a comparison of pilot plant results with those obtained in commercial operation. The Cretaceous plant at the Hill Annex mine of the Jones & Laughlin Steel Corp. was designed with a wet autogenous mill for grinding low grade iron ore so that it could be concentrated by spirals and flotation cells. The plant, on the west end of the Minnesota's Mesabi Range, went into operation in June 1961, and preliminary operating and metallurgical information describing the performance of this mill can now be given. The crude is lean ore from the Cretaceous iron foundation. This formation is a beach deposit of Cretaceous age that overlies the Precambrian direct shipping and concentrating ores. This rock in nature is not extremely hard but is quite resilient, resisting blasting in mining and size reduction in milling. It contains hematite as water-rounded particles and other fragments of the underlying iron formation and adjacent rocks cemented together by a high alumina-silica ferruginous matrix. It is interspersed with hard dense hematite agglomerates and also contains granite pebbles and boulders that were not cleaned off during removal of the surface. It has a 3.48 sp gr and in the stockpile the material consists of frag-

Jan 1, 1962

By L. H. Robinson

A proposed method of drilling utilizes sequential detonation of two types of explosive charges delivered to the hole by a conventional drilling fluid through pipe. A shaped charge first produces a long thin hole. A second charge, called a gauging charge, is pumped into the thin hole, explodes, and enlarges it to full gauge. In one suggested configuration, the explosives are contained in cylindrical capsules 4- to 5-ft long. A drilling head is positioned 2- to 3-ft off bottom. When a capsule is pumped to the bottom of the hole and stops, pressure inside the drill pipe increases and differential pressure detonates the explosive. Primacord along the length of the capsule disintegrates the capsule. The debris circulates out of the hole with the drilling fluid. The gauging-charge action was examined using 2-ft cubes of Berea sandstone. The sandstone (18 per cent porosity) was vacuum-saturated with water and surrounded by concrete. To prevent reflected tensile pulses, the acoustical impedance of the concrete matched that of the sandstone. A 750-psig pressure was applied to a drilling fluid within a shaped-charge-formed hole before detonating the gauging charge. In these tests, 190 gm of rock were removed for each gram of explosive detonated. A similar series of experiments on low-porosity (0.40 per cent) metamorphic limestone provided a more rigorous test. Extensive fracturing from the gauging-charge action prevented an estimate of the volume of the expanded hole. The diameter of the hole was irregular, ranging from about 2 to 4 in, or about fivefold larger than the hole created by the shaped charge. INTRODUCTION In the past, explosives have found a varied but somewhat limited use in the oil field. An early well stimulation technique, still in use today, in vo lves shooting ni troglycerin to en large the borehole and to increase matrix permeability near the wellbore. Bullets and jets are now the conventional method of perforating casing and tubing. Detonations are frequently used to "back off" or "shoot off" stuck pipe and, of course, seismo-graphic work has long depended on explosive-generated pulses to find attractive earth structures. Efforts to use explosives in drilling operations have received limited examinations1-3 which, in one respect, is surprising because explosives offer one way to transmit large amounts of energy directly to the bottom of the hole. Recently, Ostrovskii l described a Russian method of drilling with explosives that utilizes small capsules containing explosives which are pumped into the mud stream to the bottom of a borehole. As the capsules leave the end of the drill pipe, a detonation mechanism is armed. Impact detonates the explosive. In another configuration, two liquids (an oxidizing agent and fuel) in the capsule are separated by a frangible membrane. Separately, the liquids are nonexplosive. Near the bottom of the drill pipe, the capsule passes through a narrow constriction which ruptures the membrane. The mixing of the liquids produces an explosive. Impact is again used to detonate the explosive. About the time Ostrovskii was developing his method, Humble Oil & Refining Co. was independently doing research on another explosive drilling concept based on the sequential detonation of two types -of explosive charges. The proposed technique consisted of alternately pumping a shaped charge and then a "gauging charge" down a well. The shaped charge should drill a long, tapered hole, and the gauging charge should expand it to full gauge. This paper presents the visualized drilling concept and gives results of laboratory work which showed that sequential firing of charges can form hole at an attractive charge-to-rock removal ratio. An important finding was that increased environmental pressure, which is to be expected in wells, increases rock removal efficiency of the gauging charge.

Jan 1, 1966

By C. K. Donoho

SILICON is used in almost all commercial steels; up to about 0.20 pct in killed wrought steels and 0.50 pct in steel castings. Above about 0.50 pct in wrought steels and 0.70 pct in cast steels, silicon is considered an alloy. As an alloy, silicon is useful for several purposes: (I) for its effect on magnetic properties of parts for electrical apparatus; (2) for increasing the yield strength of carbon and low-alloy steels without too much sacrifice of ductility and weldability; (3) for adding hardness and toughness to spring and chisel steels; (4) for adding resistance to scaling and carburization to heat-resistant steels; and (5) for its graphitizing effect in graphitic steels. In acid electric steels for casting we are principally interested in the effect listed second; i.e., increase of strength with minimum sacrifice of ductility.

Jan 1, 1947

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By A. F. Giamei, E. J. Freise

A discussion of the various factors affecting the accuracy of volume fraction determination by the direct comparison X-ray diffraction method is presented. To minimize errors introduced by nonrandomization effects such as preferred orientation and large grain size, as well as errors introduced by statistical effects, an iterative mathematical analysis is introduced. This analysis is applied to all observable diffractio~ spectra from a given specimen by means of computer techniques and is statistically superior to the standard direct comparison technique which utilizes only one or tm sets of intensity spectra. The computer program also presents a graphical interpretation of- the results which enables the investigator to visualize and readily assess the scatter in volume fraction estimates caused by deviations from randomness. Finally, the iterative analysis is applied to experimental data collected from a series of plain carbon steels in both the as-received and spheroidized conditions to determine the volume fraction of cemen-tite present in each case. The results show markedly good agreement with chemical analyses for all spheroidized specimens. In theory, quantitative X-ray diffraction is a power-ful analytical technique for precise determination of the volume fractions of various phases present in a multiphase poly crystalline aggregate. There are two generally used methods; both utilize the fact that the intensity of a diffraction line of a particular phase is a function of volume fraction of that phase present in the aggregate. The more common method is the so-called internal standard technique where a known amount of standard substance is mixed with the aggregate containing the unknown. The resulting ratio of the intensity of a particular diffraction line of the unknown to the intensity of a diffraction line from the standard is used to find the weight fraction of unknown material by reference to the intensity data obtained from a previously prepared set of standards containing the same amount of standard material. The details of this technique are outlined in standard works on X-ray diffraction.' The disadvantages of the technique are that it requires the use of powder specimens and that the powder mixture must be homogeneous near the surface to the maximum effective beam depth. The alternative technique is the direct comparison method in which the ratio of the intensity of a diffraction line of a phase in the aggregate to the intensity of a second-phase diffraction line yields the ratio of the volume fractions of each phase present. This method has been applied most extensively to the determination of the percentage of retained austenite in martensitic steels and to determining the amounts of hcp and fcc allotropic modifications in pure cobalt5 and the amounts of hexagonal and rhombohedra1 modifications in graphite.8 This method is applicable to bulk as well as powder aggregates and is the technique which will be considered in the following text. It is the purpose of the present communication to show that by combining the results of X-ray diffrac-tometry with the use of high-speed digital computers the results of the direct comparison quantitative X-ray analysis technique can be optimized by using all of the data available on a diffraction pattern. THEORETICAL DISCUSSION In optimizing any quantitative X-ray diffraction experiment, the problem of accuracy vs time to collect and analyze the experimental data arises. For any method to be practical, it is required that both experimental and analytical procedures are reasonably short. In most of the previous work performed by the direct comparison method, intensity data from only one or two sets of peaks were used to calculate the volume fraction of phases present in the aggregate. Consequently, rather long-time experimental measurements are required to assure that the intensity data are sufficiently accurate to justify the use of one or two sets of data. By using computer techniques to analyze the experimental data it becomes feasible to use all of the available data on a diffraction pattern. By so doing, the time spent in measuring any one diffraction maxima can be appreciably reduced. Although this results in poor counting statistics for any one maxima, the number of data points available for analysis is greatly increased. Based on the above discussion, it will be assumed that a continuous scanning counter-diffractometer technique will be used to collect intensity data from a two-phase mixture. The integrated intensity of the ith diffraction line from the a phase in the aggregate is given by:'" where is the volume fraction of the a phase, The various quantities in Eq. [la] are angular independent while those in [lb] depend on the hkl spectrum of a particular phase. The meaning of the individual quantities in Eqs. [la] and [lb] are given in Appendix 1. It is convenient at this point to outline briefly the factors which will affect the measured intensity of any one hkl spectrum. a) Extinction effects arise from two independent experimental conditions. Primary extinction arises from a high degree of crystal perfection and results in spectra having lower intensity than predicted by Eq. [I]. Any treatment, such as powdering, which reduces

Jan 1, 1968

By S. Brunauer

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

Jan 1, 1963

By John A. Church

IT is a well-known fact that under similar conditions a ton of pig iron can be made from any ore with less fuel when charcoal is used than when coke or anthracite is employed for heating. The cause of this superiority is entirely undiscovered, and no explanation has yet been offered which has won even temporary acceptance. Such as they are the hypotheses heretofore presented are of two general kinds, and they come from those two divisions of the working force which are so often antagonistic in all professions, the scientific and the practical men. The theory of the scientific men is drawn from the chemical reactions which are known to go on in the furnace, and it is well expressed in a recent paper by Prof. Akerman, of the Stockholm (Sweden) School of Mines. It makes the superiority of charcoal as a fuel in the blast furnace to depend upon its quick and thorough reduction of carbonic acid. This property belongs to charcoal in virtue of its porous structure. Its cells have a diameter of only one twenty-four hundredth of an inch, and one grain of charcoal has been computed to have a surface of two and four-tenths square feet. According to the theory in question, carbonic acid is formed by the first impact of the air upon the fuel; but in charcoal furnaces the acid is immediately reduced to oxide by taking the necessary amount of carbon into combination, and the gas reaches its highest reducing power even in the near vicinity of the tuyeres. Coke, being harder, does not produce so strong a reducing gas in that part of. the furnace. Carbonic acid is formed as in the case of charcoal, and remains longer before its reduction to oxide is completed. Anthracite is the

Jan 1, 1879

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'" Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence.

Jan 1, 1955

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By H. H. Uhlig

SINCE its first mention in the literature in the eighteenth century1,2 the phenomenon of passivity in metals has stimulated much speculation and attendant controversy as to its nature and cause. No one of the numerous theories so far proposed has been generally accepted. ? Faraday,7 in 1836, associated the passivity of iron with a protective film over the surface of the metal, which materially prevents or slows down reaction with corrosive environments. His theory was that oxidizing acids like nitric acid form an unstable oxygen or oxide layer over the iron surface, which protects the underlying metal from further attack. This concept was simple yet plausible, and without alteration has frequently been assigned in present-day discussions as explanation of the passivity of many metals. With the advent in recent times of stainless steels, it is not surprising that this oxide film theory of passivity proposed by Faraday has been used to explain the phenomenal corrosion resistance of stainless steels and other passive alloys. The passive alloys, such as the chrome-iron alloys, are supposedly covered with a protective oxide film, which forms on exposure of the alloy to air, is extremely stable and self-healing, and accounts for the remarkable resistance of these alloys to corrosion. Within the past few years, several investigators, following the theory of film protection, have attempted to gauge the resistance of the supposed film on steels. Brennert8 and Donker and Dengg9 determined the poten-tial at which a negative ion (e.g., Cl-) moving in an electric field reacted with the metal anode, as detected by increased current flow or change in potential of the steel electrode in an electrolytic cell. The potential corresponding to reaction Brennert called the film break-through potential.

Jan 1, 1939

By Harry A. Roe

The power drag scrapers and the slackline cableway excavator have been called "long-range excavators." Broadly, their field of usefulness is restricted to work in which their long range of action permits them to operate economically, and which other, possibly more conventional, excavating units cannot do. Both of these machines dig or lift material and transport it to a remote dumping point. They combine these two functions in a single machine, nearly always in a single straight-line motion. The purpose of this paper is to examine the important features that distinguish the machines in this group from each other, as well as from other groups. The Machines The "power drag scraper" is a long-range excavating machine that employs a bottomless drag scraper operated back and forth between digging and dumping points by two haulage cables. The typical arrangement is that of Fig. 1. This is the "slusher" of the underground mine, as well as the "dragline scraper" of the sand and gravel industry, and other open-pit mining operations.

Jan 1, 1938

By Harry A. Roe

The power drag scrapers and the slackline cableway excavator have been called "long-range excavators." Broadly, their field of usefulness is restricted to work in which their long range of action permits them to operate economically, and which other, possibly more conventional, excavating units cannot do. Both of these machines dig or lift material and transport it to a remote dumping point. They combine these two functions in a single machine, nearly always in a single straight-line motion. The purpose of this paper is to examine the important features that distinguish the machines in this group from each other, as well as from other groups. The Machines The "power drag scraper" is a long-range excavating machine that employs a bottomless drag scraper operated back and forth between digging and dumping points by two haulage cables. The typical arrangement is that of Fig. 1. This is the "slusher" of the underground mine, as well as the "dragline scraper" of the sand and gravel industry, and other open-pit mining operations.

Jan 1, 1938